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Thesis (MSc (Mathematics))--University of Stellenbosch, 2009. / ENGLISH ABSTRACT: Packed beds are widely used in industry to improve the total contact area between two substances in a multiphase process. The process typically involves forced convection of liquid or gas through either structured or dumped solid packings. Applications of such multiphase processes include mass transfer to catalyst particles forming the packed bed and the adsorption of gases or liquids on the solid packing. An experimental study on the determination of air flow pressure drops over different packingmaterialswas carried out at the Telemark University College in Porsgrunn,Norway. The packed bed consisted of a cylindrical column of diameter 0.072m and height 1.5m, filled with different packingmaterials. Air was pumped vertically upwards through a porous distributor to allow for a uniform inlet pressure. Resulting pressure values were measured at regular height intervals within the bed. Due to the geometric nature of a Raschig ring packing wall effects, namely the combined effects of extra wall shear stress due to the column surface and channelling due to packing adjacent to a solid column surface, were assumed to be negligible. Several mathematical drag models exist for packed beds of granular particles and an important question arises as to whether they can be generalized in a scientific manner to enhance the accuracy of predicting the drag for different kinds of packing materials. Problems with the frequently used Ergun equation, which is based on a tubular model for flow between granules and then being empirically adjusted, will be discussed. Some theoretical models that improve on the Ergun equation and their correlation with experimental work will be discussed. It is shown that a particular pore-scale model, that allows for different geometries and porosities, is superior to the Ergun equation in its predictions. Also important in the advanced models is the fact that it could take into account anomalies such as dead zones where no fluid transport is present and surfaces that do neither contribute to shear stress nor to interstitial form drag. The overall conclusion is that proper modelling of the dynamical situation present in the packing can provide drag models that can be used with confidence in a variety of packed bed applications. / AFRIKAANSE OPSOMMING: Gepakte materiaal strukture word in die industrie gebruik om die kontak area tussen twee stowwe in meervoudige faseprosesse te vergroot. Die proses gaan gewoonlik gepaard met geforseerde konveksie van ’n vloeistof of ’n gas deur gestruktureerde of lukrake soliede gepakte strukture. Toepassings van sulke meervoudige faseprossese sluit onder andere in die massa-oordrag na katalisator partikels wat die gepakte struktuur vorm of die absorpsie van gasse of vloeistowwe op die soliede gepakte elemente. ’n Eksperimentele ondersoek oor die drukval van veskillende gepakte elemente in ’n kolom is gedoen by die Telemark University College in Porsgrunn, Noorweë. Die gepakte struktuur het bestaan uit ’n kolommet ’n diameter van 0.072m en ’n hoogte van 1.5m. Lug is vertikaal opwaarts gepomp deur ’n poreuse plaat wat gesorg het vir ’n benaderde uniforme snelheidsprofiel. Die druk is toe op intervalle deur die poreuse struktuur gemeet. In die studie is die effekte van die eksterne wande, nl. die bydrae van die wand se wrywing en die vorming van kanale langs die kolom wand, as weglaatbaar aanvaar. Daar bestaan baie wiskundige dempingsmodelle vir gepakte strukture wat uit korrels saamgestel is. ’n Belangrike vraag kan dus gevra word, of laasgenoemde modelle veralgemeen kan word op ’n wetenskaplike manier om die demping deur verskillende gepakte strukture akkuraat te kan voorspel. Probleme wat ontstaan het met die wel bekende Ergun vergelyking, wat gebaseer is op ’n kapillêre model en wat toe verder aangepas is deur empiriese resultate van uniforme sfere, sal bespreek word. Teoretiesemodelle wat verbeteringe op die Ergun vergelyking voorstel sal bespreek word en vergelyk word met eksperimentele data. Daar word ook gewys dat ’n spesifieke porie-skaal model, wat aanpasbaar is vir verskillende geometrieë en porositeite, in baie gevalle beter is as die Ergun vergelyking. ’n Ander baie belangrike aspek van gevorderde modelle is die moontlikheid om stagnante gebiede in die gepakte strukture in ag te neem. Laasgenoemde gebiede sal die totale kontak area sowel as die intermediêre vorm demping verlaag. Die gevolgtrekking is dat wanneer deeglike modulering van dinamiese situasies in die industrie gedoen word kan dempings modelle met vertroue op ’n verskeidenheid gepakte strukture toegepas word.

Made available in DSpace on 2016-05-17T16:51:40Z (GMT). No. of bitstreams: 0 Previous issue date: 2015-10-16. Added 1 bitstream(s) on 2016-05-17T16:55:27Z : No. of bitstreams: 1 000863489_20171010.pdf: 270564 bytes, checksum: 14ae6d49755d9bd4f1165d0581118e98 (MD5) Bitstreams deleted on 2017-10-16T12:45:42Z: 000863489_20171010.pdf,. Added 1 bitstream(s) on 2017-10-16T12:46:28Z : No. of bitstreams: 1 000863489.pdf: 2384161 bytes, checksum: 21b3016117fd918faa1b92c15a40eb86 (MD5) / A produção de aluminas com distribuição de tamanho e volume de poros controlados pela separação de fases líquido-sólido é um assunto emergente na área de cerâmicas porosas. As aluminas foram produzidas pelo processo sol-gel acompanhado de separação de fases, usando o óxido de polietileno (PEO) como agente indutor na separação de fases e o óxido de propileno para a gelatinização, para isso foram estabelecidas condições de controle cinético e termodinâmico desses eventos, através do controle do tempo de agitação e temperatura no meio reacional. Foram otimizadas rotas de síntese através do ajuste dos parâmetros de preparação variando a concentração do agente direcionador de poros PEO durante a transição sol-gel. Esta transformação foi acompanhada in-situ por SAXS revelando que o crescimento de objetos fractais com dimensionalidade de 1,7, que é característico do mecanismo e agregação controlado pela difusão. A calcinação em 700°C possibilitou a produção de aluminas da fase gama (-Al2O3) com textura porosa formada por macro e mesoporos. O uso do agente direcionador de poros PEO em proporção molar entre 0,01-0,07 mostrou-se eficiente no ajuste da macro-mesoporosidade. Entretanto quando se emprega proporções molares de PEO acima de 0,07 obtém-se apenas famílias de mesoporos com um decaimento do volume específico de poros quando a proporção molar aumenta de 0,08 para 0,1. Estas aluminas mesoporosas apresentaram maior área superficial especifica (Área BET máximo de  305 m²/g) e uma melhor relação OH/-O-Al em comparação com as macro-mesoporosas. / The production of alumina with volume and size distribution of pores controlled by phase separation induced by the addition of the polymer polyethylene oxide (PEO) during synthesis is an emerging issue in the area of functional ceramics. The aluminas were produced by the sol-gel process followed by phase separation, and the PEO as inducing agent phase separation and propylene oxide to gelation. Conditions for kinetic and thermodynamic control over these events were kept by controlling the stirring time and temperature in the reaction medium. Synthesis routes have been optimized by adjusting the preparation parameters varying the concentration of pores directing agent (PEO) during sol-gel process. This transformation was accompanied by in-situ SAXS and the results reveal the growth typical of fractal objects starting from a diluted solution, whose dimensionality in the Porod region was 1,7, characteristic of aggregation controlled by diffusion and the distances between the growing particles is around 2,95 nm. Gamma alumina (-Al2O3) with diversified porous texture and macro-mesopores was obtained with thermal treatment up to 700 ° C, being supported by several techniques. The macro-mesoporosity can be adjusted by PEO driver pores agent in a molar ratio from 0,01 to 0,07. Molar ratios of PEO above 0,07 produces only mesopores, decreasing the cumulative volume of this pores when the molar ratio increases from 0,08 to 0,1. These mesoporous aluminas had higher specific surface area (BET Area  305 m² / g) and better ratio OH/O-Al compared to the macro-mesoporous.

Orientador: Regina Célia Galvão Frem / Banca: Sidney Jose Lima Ribeiro / Banca: Grégoire Jean-François Demets / Resumo: Segundo a IUPAC, MOFs (Metal-Organic Frameworks) são definidos como polímeros de coordenação com uma estrutura aberta contendo cavidades potencialmente vazias. As MOFs podem ser sintetizadas utilizando íons lantanídeos como centros metálicos (LnMOFs) e por essa razão, apresentam luminescência somada às demais propriedades desta classe de materiais porosos. Dentro desse contexto, o objetivo deste trabalho foi a obtenção de LnMOFs visando aplicação na área de sensoriamento químico via luminescência. Os compostos foram sintetizados a partir dos cloretos de térbio (III), európio (III) e samário (III) hexahidratados (precursores metálicos) e dos ligantes ácidos malônico e 3,5-pirazoldicarboxílico. Os compostos de térbio e ligantes foram sintetizados em diferentes pHs, sendo que os valores iguais a 2, 4 e 5 conduziram a formação dos materiais TBM2, TBM4 e TBM5, respectivamente. Os sólidos de európio e samário foram sintetizados em pH igual a 5 (compostos EUM5 e SMM5, respectivamente). As sínteses foram realizadas utilizando micro-ondas e estufa solvotérmica. As amostras TBM4 e TBM5 obtidas via micro-ondas se organizam na forma de partículas com tamanhos entre 0,5 - 2 μm e morfologia esférica. Ensaios de caracterização demonstraram que se tratava do mesmo composto, exceto uma maior rugosidade nas partículas do TBM5. A cristalinidade do material foi baixa devido ao curto tempo de síntese, no entanto utilizando síntese solvotérmica (mais lenta) foi possível aumentar a cristalinidade. ... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: According to IUPAC, MOFs (Metal-Organic Frameworks) are coordination polymers with an open structure containing potentially empty voids. MOFs can be synthesized using lanthanide ions as metal centers (LnMOFs) and therefore have luminescence added to the other properties of this porous materials class. In this context, the objective of this work was to obtain LnMOFs for chemical sensing application via luminescence. The compounds were synthesized from terbium (III), europium (III) and samarium (III) chlorides hexahydrates (metal precursors) and the malonic and 3,5-pyrazoledicarboxylic acid linkers. The compounds with terbium plus linkers were synthesized at different pHs, with values of 2, 4 and 5 leading to the formation of TBM2, TBM4 and TBM5 materials, respectively. The europium and samarium solids were synthesized at pH = 5 (compounds EUM5 and SMM5, respectively). The syntheses were microwave and solvothermic assisted. The TBM4 and TBM5 samples via microwave-assisted synthesis are organized in the form of particles with sizes between 0.5 - 2 μm and spherical morphology. Characterization tests showed both are the same compound, except for a greater roughness in the TBM5 particles. The crystallinity of the material was low due to the short synthesis time; however, by using solvothermic-assisted synthesis (slower) it was possible to increase the crystallinity. There are characteristic bands of both ligands in the infrared vibrational spectroscopy, as well as band displacement... (Complete abstract click electronic access below) / Mestre

En chromatographie en phase gazeuse, la miniaturisation ouvre la voie pour de nouveaux appareils portables, consommant peu d'énergie et de gaz et permettant des analyses directement sur site en évitant ainsi le transport d'échantillons. Depuis les années 70, l'essentiel des travaux s'est focalisé sur les hydrocarbones les plus lourds, avec 5 atomes de carbones ou plus. Ce travail expose le développement de nouvelles phases stationnaires de silice mésostructurées pour la séparation des alcanes légers (avec moins de 5 atomes de carbones) dans des colonnes micro-fabriquées, suivant deux procédés diffrérents : i) le dépôt dynamique in-situ d'un sol directement dans les colonnes capillaires ou micro-fabriquées, ou ii) le dépôt couche-par-couche de nanoparticules de silices (SNPs) sur les micro-colonnes. L'influence des paramètres du dépôt sol-gel sur l'épaisseur finale du de la phase stationnaire a été étudiée sur des colonnes capillaires courtes. En modifiant la nature et la concentration de l'agent structurant, il a été possible d'obtenir différentes mésostructures plus ou moins ordonnées et de modifier le pouvoir rétentif de la colonne. Curieusement, les structures les moins organisées ont montré la rétention la plus importante vis-à-vis des alcanes, comparable à celle de colonnes commerciales, mais pour une épaisseur de phase stationnaire 30 fois plus faible. Le procédé a été adapté avec succès aux colonnes micro-fabriquées. Les colonnes obtenues montrent des efficacités de séparation prometteuses, et le plus grand nombre de plateau théorique par mètre (th.p./m) rapporté à ce jour pour l'éthane (7500 th.p./m). Finalement, un procédé alternatif par dépôt couche-par-couche a été étudié pour déposer directement des nanoparticules de silice comme phase stationnaire dans les micro-colonnes. Ce procédé a d'abord été évalué pour des SNPs commerciales non poreuses. Puis il a été appliqué avec succès au dépôt de SNPs mésostructurées, synthétisées au laboratoire, et validé pour le dépôt pleine-plaque de 35 micro-colonnes en simultané. Dans l'ensemble, ce travail démontre l'efficacité des phases stationnaires en silice mésostructurée pour la séparation des alcanes légers par des colonnes micro-fabriquées / Miniaturization in Gas Chromatography opens the way to low cost, low gas and low power consumption portable devices, which offer in-situ analysis and avoid tedious transport of samples to laboratories. Since the first micro-fabricated column in the late 1970’s, the main focus was directed to the separation of heavy molecular weight hydrocarbons, with 5 or more carbon atoms. In this work, we have developed sol-gel mesotructured silica stationary phases for the separation of light alkanes (from one to 5 carbon atoms) in micro-fabricated columns, following two different procedures: i) the deposition of a sol-gel thin film by dynamic coating directly into the GC capillary or on micro-fabricated columns or ii) the layer-by-layer (LbL) deposition of silica nanoparticles (SNPs) on micro-fabricated columns. The influence of the sol-gel process coating parameters on the final thickness of the stationary phase was studied on short capillary columns. Various ordered or disordered mesostructures were yielded by varying the nature and the concentration of the structure directing agent (SDA), thus allowing the obtention of columns with different retention strengths. Interestingly, the less organized layers led to the columns with the highest retention, comparable with commercial columns for stationary phases being 30 times thinner. The process was successfully transposed to micro-fabricated columns. The obtained micro-columns showed promising efficiencies and the highest number of theoretical plates per meter (th.p./m) reported to date for ethane (7500 th.p./m). Finally, we investigated an alternative way to coat GC micro-columns directly with mesostructured silica nanoparticles using an LbL process. The process was first evaluated for commercial non porous SNPs. Then it was successfully applied to mesostructured custom SNPs and further validated for the full-wafer simultaneous coating of 35 columns. Overall, this work demonstrated the use of mesostructured silica as an effective stationary phase for light alkane’s separation on GC micro-fabricated columns

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / O presente trabalho teve como objetivo avaliar volumetricamente a presença de poros em três cimentos obturadores. Para a análise de porosidade, quatro cilindros de cada cimento foram preparados e escaneados usando um microtomógrafo de alta resolução (Skyscam 1174, Kontich, Bélgica). O cálculo da porosidade foi realizado por meio de análise de imagens digitalizadas dos blocos de cimentos. Os quais foram microtomografados para criação de modelos tridimensionais. A presença de poros e vacúolos foi então avaliada por inferência do software CT analiser. Os resultados mostraram que o i-Root SP teve o menor índice de porosidade (0,07%), enquanto o AH plus e o MTA Fillapex não apresentaram diferenças estatisticamente significativas entre si (p≥0,05). Apesar dos resultados para o índice de porosidade total do MTA Fillapex e do AH plus não terem diferenças significativas(p>0,05), os achados do presente trabalho mostraram que o MTA fillapex obteve resultados significativamente maiores nos volumes médios individuais dos poros internos que o Ah plus e o i-Root SP. Os resultados foram tabulados e analisados estatisticamete através do teste Anova ao nível de significância de 5%. / This study aimed to evaluate the presence of pores volumetrically in three sealers. For the analysis of porosity, four-cylinder of each cement were prepared and scanned using a high resolution Micro-CT scanner (Skyscam 1174, Kontich, Belgium). The porosity calculation was performed by analysis of digitized images of cement blocks. Which were scanned for creating three-dimensional models. The presence of pores and vacuoles was then evaluated by inference software CT Analiser . The results showed that the i-Root SP had the lowest porosity index (0.07%), while the AH Plus and MTA Fillapex showed no statistically significant differences between groups (p ≥ 0.05). Although the results for the index of total porosity Fillapex MTA and AH Plus did not have significant differences (p> 0.05), the findings of this study showed that the MTA fillapex scored significantly higher in the average volume of individual internal pores that Oh the plus and i-Root SP. The results were tabulated and analyzed estatisticamete by ANOVA at a significance level of 5%.

Neste trabalho, foram preparadas resinas contendo o grupo sulfofosforila a partir de copolímeros de estireno e divinilbenzeno (Sty-DVB). O copolímero sintetizado Sty-DVB foi modificado com PCl3 e AlCl3 durante 15 horas de reação em diferentes condições de temperatura e razão molar P/Al. Os copolímeros fosforilados obtidos nas diferentes condições tiveram o teor de fósforo dosado por espectrofotometria para avaliar a extensão da modificação, sendo também caracterizados por espectroscopia na região do infravermelho (FTIR), termogravimetria, microscopia óptica (MO) e microscopia eletrônica de varredura (MEV). A resina fosforilada otimizada de maior percentual de fósforo incorporado foi obtida empregando-se o tempo de reação de 15 horas, temperatura de 50 C e razão molar P/Al = 1/1,5. Essas condições otimizadas de fosforilação foram empregadas para obtenção da resina fosforilada RMF em larga escala. A resina fosforilada foi modificada com CS2 à temperatura ambiente em diferentes condições de tempo e quantidade molar adicionada do agente de sulforação (CS2). A resina sulfofosforilada otimizada de maior percentual de enxofre incorporado, determinado por análise elementar, foi obtida empregando-se o tempo de reação de 6 dias e adição de 15 mL de CS2, à temperatura ambiente. As resinas sulfofosforiladas foram também caracterizadas por FTIR, termogravimetria, MO e MEV, e tiveram a capacidade biocida avaliada através da determinação do número de células viáveis utilizando a técnica de contagem em placa junto à suspensão de Escherichia coli (ATCC25922TM, tipo selvagem). A maior capacidade biocida foi observada na resina sulfofosforilada com maior teor de enxofre incorporado / In this work, resins containing the sulfophosphoryl group were prepared from synthesized styrene and divinylbenzene (Sty-DVB) copolymers. The synthesized Sty-DVB copolymer was modified with PCl3 and AlCl3 for 15 hours under different conditions of temperature and P/Al molar ratio. The phosphorylated copolymers obtained under different conditions were assayed by spectrophotometry to measure the content of incorporated phosphorus and the extent of modification, and also characterized by infra-red spectrometry (FTIR), thermogravimetry, optical microscopy (MO) and scanning electron microscopy (SEM). The phosphorylated resin with the highest content of phosphorus was obtained by using the time of 15 hours, temperature of 50 C and P/Al molar ratio = 1/1.5. These optimized conditions were employed to obtain phosphorylated resin RMF in large scale. The phosphorylated resin was modified at room temperature with CS2 under different conditions of time and the molar amount added of the sulforation agent (CS2). The sulfophosphorylated resin with the highest content of sulfur, determined by elemental analysis, was obtained by using the reaction time of 6 days and addition of 15 mL CS2, at room temperature. The sulfophosphorylated resins were characterized by FTIR, thermogravimetric analysis, MO e MEV, and had the biocidal activity evaluated by determining the number of viable cells of Escherichia coli (ATCC25922TM, wild type) using the technique of plate counting. The sulfophosphorylated resin with the highest biocidal activity was the resin obtained with highest content of incorporated sulfur

No contexto das teorias de perturbação estocástica, analisamos a acurácia de dois modelos poroelásticos lineares aplicados a meios porosos altamente heterogêneos sujeitos as incertezas na permeabilidade e nas constantes elásticas. Os modelos poroelásticos completamente e fracamente acoplados analisados surgem caracterizados pelo grau de intensidade de acoplamento entre a hidrodinámica governante da percolação o do fluido e a poromecânica que rege as deformações da matriz porosa. Novas equações efetivas para os momentos das soluções são obtidas fazendo uso de técnicas de expansão assintótica. À luz da teoria de perturbação, são estabelecidas hipóteses simplificadoras que elucidam o domínio de validade do modelo fracamente acoplado, amplamente utilizado nos simuladores de Reservatórios de Petróleo, na presença de heterogeneidades e correlação nos coeficientes poroelásticos. Simulações computacionais do processo de extração primária de petróleo são realizadas utilizando técnicas de Monte Carlo em conjunção com métodos de elementos finitos. Resultados numéricos obtidos confirmam claramente a conjectura estabelecida pela teoria de perturbação relacionada com a inacurácia do modelo fracamente acoplado na presença de variabilidade nas constantes elásticas. A metodologia empregada permite quantificar a distância entre os dois modelos poroelásticos, e consequentemente, propor a escolha do modelo apropriado para diferentes condições de carregamento e variabilidade da formação geológica. / In the context of the stochastic perturbations theories we analyze the accuracy of two linear poroelastic models applied to highly heterogeneous porous media subject to uncertainties in the permeability and the elastic constants. The poroelastic models completely and weakly coupled analized arise characterized by the degree of intensity coupling between the hydrodinamics, governor of the percolation of the fluid and poromechanics which governs the deformation of the porous matrix. New equations for the moments of effective solutions using techniques of asymptotic expansion. In light of the perturbation theory are set simplifying assumptions that clarify clearly the domain of validity of weakly coupled model, widely used in simulation of oil reservoirs in the presence of heterogeneities and correlation in poroelastic coefficients. Computational simulations of the primary extraction of oil process are carried out using Monte Carlo techniques in conjunction with finite element methods. Results obtained clearly confirm the conjecture established by the perturbation theorie related with the inaccuracy of the weakly coupled model in the presence of variability in the elastic constants. The methodology used allows to quantify the distance between the two poroelastics models and therefore propose the appropriate model for different conditions of loading and variability of the geological formation.

Made available in DSpace on 2014-10-09T12:50:10Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:02:01Z (GMT). No. of bitstreams: 1 10557.pdf: 8187927 bytes, checksum: d75a44c7b8aac58fb39836dd7d91e5d8 (MD5) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP / FAPESP:03/10049-5

Made available in DSpace on 2014-10-09T12:55:20Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:07:11Z (GMT). No. of bitstreams: 0 / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Dissertação (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP / FAPESP:06/52700-2