Diffusive mass transport within porous SOFC components is explored using two modeling approaches that can better inform the SOFC electrode design process. These approaches include performance metrics for electrode cross-sectional design and a fractal approach for modeling mass transport within the pore structure of the electrode reaction zone. The performance metrics presented are based on existing analytical models for transport within SOFC electrodes. These metrics include a correction factor for button-cell partial pressure predictions and two forms of dimensionless reactant depletion current density. The performance impacts of multi-dimensional transport phenomena are addressed through the development of design maps that capture the trade-offs inherent in the reduction of mass transport losses within SOFC electrode cross-sections. As a complement to these bulk electrode models, a fractal model is presented for modeling diffusion within the electrochemically active region of an SOFC electrode. The porous electrode is separated into bulk and reaction zone regions, with the bulk electrode modeled in one-dimension based on the dusty-gas formalism. The reaction zone is modeled in detail with a two-dimensional finite element model using a regular Koch pore cross-section as a fractal template for the pore structure. Drawing on concepts from the analysis of porous catalysts, this model leads to a straightforward means of assessing the performance impacts of reaction zone microstructure. Together, the modeling approaches presented provide key insights into the impacts of bulk and microstructural geometry on the performance of porous SOFC components.

Past nuclear weapon production activities have left a significant legacy of uranium (U) contamination in the vadose zone (VZ) of the Department of Energy (DOE) Hanford Site. This U is a source of groundwater (GW) contamination. There is a concern that elevated U concentration would slowly infiltrate through the VZ, reach the GW water table, and then end up in nearby rivers and lakes. Remediation of U-contaminated low moisture content soil is a challenging task considering the VZ depth, where contamination is found between 70 and 100 m below the ground surface, and the formation of highly soluble and stable CaUO2CO3 complexes is influenced by Hanford’s soil rich in carbonate. Injection of reactive gasses (e.g., NH3) is a promising technology to decrease U migration in through the VZ. The NH3 injection creates alkaline conditions that would alter the pore water chemistry (e.g., dissolving some aluminosilicates). Over time as the pH neutralizes, U(VI) could precipitate as uranyl mineral (e.g., Na-boltwoodite). Also, the dissolved U(VI) could be incorporated into the structure of some mineral phases or be coated by non-U minerals. These chemical reactions could control the U(VI) mobility to the GW. However, there is a lack of knowledge on how the VZ pore water constituents (e.g., Si, Al3+, HCO3-, and Ca2+) would affect U(VI) removal/precipitation in alkaline conditions. This study quantified the role of the major pore water constituents on the U(VI) removal and evaluated the uranyl minerals that could precipitate from a variety of SPW solutions. Results showed that the percentage of U(VI) removal was controlled by Si/Al ratios and Ca2+ concentration regardless of HCO3- concentration tested. XRD revealed the presence of uranyl minerals by analyzing precipitates formed from SPW solutions, but none of them were identified as uranyl silicates as expected from speciation modeling. The SEM images displayed dense amorphous regions high in silica content, where EDS elemental analysis unveiled higher U atomic percentage in some samples. U(VI) silicate and carbonate minerals were predicted by the speciation modeling.

Apresentamos cálculos de estrutura eletrônica de oligotiofenos e oligoanilinas conectados a contatos metálicos. Diversos aglomerados de ouro e acoplamentos com as moléculas orgânicas foram testados. Expressões analíticas para a função de transmissão, de acordo com a teoria de Landauer, foram obtidas por meio de um modelo tight-binding, juntamente com resultados numéricos da teoria do funcional da densidade (DFT). O pacote computacional Gaussian 03 foi empregado para realizar os c_alculos DFT com o funcional híbrido B3LYP. Um conjunto de base misto foi escolhido: LANL2DZ para os átomo de ouro e 6-31G* para os átomos leves S, C, N e H. A geometria das cadeias orgânicas conectadas a eletrodos metálicos depende fortemente do tipo de conexão e fracamente do número de átomos representando o eletrodo. Em nossos modelos o átomo de enxofre conecta-se ao eletrodo nas geometrias bridge e atop. A principal diferença entre estes acoplamentos é uma significativa transferência de elétrons nos oligômeros ligados na forma atop. A redistribuição de carga resulta numa cadeia orgânica carregada positivamente acompanhada por uma mudança estrutural. Oligotiofenos apresentam uma distorção quinoide, enquanto que nas pernigranilinas(PE) sua alternância entre anéis quinoides e aromáticos é invertida. Um campo elétrico externo foi aplicado nos sistemas. A resposta da transmissão eletrônica _e correlacionada com o estado de oxidação das cadeias e acoplamento com os eletrodos. Nos sistemas de leucoesmeraldina (LE) e esmeraldina(EM) conectados de forma atop, o campo elétrico induz a localização dos orbitais de fronteira levando à diminuição da transmitância. Cadeias de LE e EM conectadas de forma bridge e as PE apresentam um aumento na transmissão em função do campo elétrico. Nas cadeias de PE as propriedades são menos dependentes da conexão com o eletrodo. Aplicamos uma tensão nas cadeias orgânicas forçando um alongamento, similarmente ao que acontece nos experimentos de quebra de junção. Cadeias de LE e EM conectadas de forma bridge bem como PE em ambas conexões com os eletrodos, apresentam a mesma dependência do transporte em função do estiramento. O aumento inicial da transmissão é associado à planarização da cadeia, que induz a deslocalização dos orbitais. Entretanto, o subsequente alongamento localiza os orbitais por aumentar os comprimentos de ligação, o que leva a uma baixa transmitância. Cadeias de LE e EM conectadas de forma atop são fracamente afetadas pelo alongamento. Em oligotiofenos nos dois tipos de conexão com os eletrodos, o estiramento provoca uma significativa redução da transmissão. Por este mecanismo, oligômeros mais longos apresentam valores de condutância similares aos mais curtos. / We present electronic structure and transport calculations of oligothiophenes and oligoanilines bonded to metallic contacts. Several gold clusters and couplings to the organic molecule were tested. Analytical expressions for the transmission function, within Landauer theory, were obtained by means of a tight-binding model, along with numerical results from density functional theory (DFT). The software Gaussian 03 was employed to perform DFT calculations with the hybrid functional B3LYP. A mixed basis set was chosen: LANL2DZ for gold atoms and 6-31G* for light atoms S, C, N and H. The geometry of organic chains bonded to metallic electrodes depend strongly on the type of connection with the metallic electrode and weakly on the number of atoms representing the electrode. In our models the sulfur atom connects to the electrodes in either atop or bridge geometries. The main diference between these two couplings is a significant electronic transfer on the atop bonded oligomers. The charge reorganization results in a positively charged organic part accompained by a structural change. Oligothiophenes present a quinoidal distortion, while in pernigranilines the alternation between aromatic and quinoid ring is reversed. An external electric field was applied to the systems. The electronic transmission response is correlated to the oxidation state and coupling to electrodes. On the atop bonded systems leucoemeraldine(LE) and emeraldine (EM), the electric field induces a localization of the frontier orbitals leading to a decreased transmission. Pernigranilines(PE) and bridge-bonded LE and EM present an increase of transmission as a function of the electric field. In the PE chains the properties are less dependent on the connection to the electrodes. We applied a tension on the organic chains by forcing an elongation, similarly to what happens in break-junction experiments. Bridge-bonded LE and EM, as well as PE in both types of connection to electrodes, present the same dependence of transport as function of stress. The initial increasing transmission is associated to a planarization of the chain that induces an orbital delocalization. However, the subsequent elongation localize orbitals by increasing the bond lengths and leads to a low transmission. Atop bonded LE and EM are weakly sensitive to elongation. On oligothiophenes in both types of connection to the electrodes, the stretching induces a significant decrease of transmission. By this mechanism longer oligomers present conductance values similar to small ones.

Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgico / Neste trabalho, foram estudados vÃrios tipos de escoamentos laminares de fluidos incompressÃveis Newtonianos e nÃo-Newtonianos. Isto foi feito atravÃs do estudo da interaÃÃo destes escoamentos com geometrias complexas atravÃs de modelagem computacional e da soluÃÃo numÃrica das equaÃÃes de conservaÃÃo do momento e continuidade de massa. Numa primeira etapa, a modelagem computacional de uma rede de poros foi usada para a gerar padrÃes de agregados granulares resultando de mecanismos de erosÃo-deposiÃÃo de grÃos leves. A geometria da rede de poros foi alterada dinamicamente de acordo com a transferÃncia de momento do escoamento para as partÃculas localizadas em cada vÃrtice da rede de poros. Os resultados mostraram que, para esse processo irreversÃvel, o modelo foi capaz de reproduzir padrÃes tÃpicos de processos de erosÃo bem-conhecidos. Numa segunda etapa, um separador de partÃculas semelhante à estrutura pulmonar foi proposto com base nas propriedades de escoamento em uma estrutura ramificada e nas propriedades de transporte inercial das partÃculas, quantificadas atravÃs do nÃmero de Stokes. Os resultados indicaram que a variaÃÃo dos parÃmetros de construÃÃo da estrutura ramificada leva a um regime eficiente do processo de separaÃÃo em um amplo espectro de valores do nÃmero de Stokes. Por Ãltimo, o escoamento de vÃrios fluidos nÃo-Newtonianos atravÃs de meios porosos desordenados em trÃs-dimensÃes foi estudado. Os resultados mostraram, para fluidos do tipo lei-de-potÃncia, que o escoamento pode ser descrito como uma curva universal se o nÃmero de Reynolds e a permeabilidade hidrÃulica forem redefinidos de maneira apropriada. Fluidos de Bingham tambÃm foram estudados atravÃs do modelo de Herschel-Bulkley. Neste caso, as simulaÃÃes revelaram que as interaÃÃes entre a geometria complexa do espaÃo poroso, as propriedades reolÃgicas do fluido e os efeitos inerciais do escoamento sÃo responsÃveis por uma melhora substancial da permeabilidade hidrÃulica do sistema em valores intermediÃrios do nÃmero de Reynolds. / In this work many types of incompressible laminar Newtonian and Non-Newtonian flows are studied. The interplay of these flows with complex geometries was investigated using computational modeling and numerical solution of the conservation of momentum and mass continuity equations. As a first step, the computational modeling of a network of pores was adopted to reveal the formation patterns caused by the mechanism of erosion-deposition of light grains. The geometry of the pore network was changed dynamically according to the flow momentum transfer for particles located on each vertex of the pore network. The results showed that, for this irreversible processes, the model is capable of reproducing patterns of formation of well-known erosion processes. In a second step, a particle separator inspired on the lung structure was proposed based on the flow properties in a branched structure and transport of inertial particles, quantified in terms of the Stokes number. The results indicated that the variation of construction parameters of the branched structure leads to an efficient design of the separation process in a wide range of values of the Stokes number. Finally, the flow of non-Newtonian fluids through three-dimensional disordered porous media has been studied. The results showed, for power-law fluids that the flow can de described as a universal curve if the Reynolds number and the hydraulic permeability are redefined properly. The flow of Bingham fluids was also studied using the model of Herschel-Bulkley. In this case, the simulations showed that the interaction between the complex geometry of the pore space, the rheological properties of the fluid and the inertial effects of the flow is responsible for a substantial improvement of the hydraulic permeability of the system at intermediate values of the Reynolds number.

Submitted by Renata Lopes (renatasil82@gmail.com) on 2017-03-06T18:36:40Z No. of bitstreams: 1 rafaeladeoliveiraamaral.pdf: 3948829 bytes, checksum: 00e0ed24c70d94662bfaf016bfc787cc (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2017-03-06T20:27:03Z (GMT) No. of bitstreams: 1 rafaeladeoliveiraamaral.pdf: 3948829 bytes, checksum: 00e0ed24c70d94662bfaf016bfc787cc (MD5) / Made available in DSpace on 2017-03-06T20:27:03Z (GMT). No. of bitstreams: 1 rafaeladeoliveiraamaral.pdf: 3948829 bytes, checksum: 00e0ed24c70d94662bfaf016bfc787cc (MD5) Previous issue date: 2014-02-21 / FAPEMIG - Fundação de Amparo à Pesquisa do Estado de Minas Gerais / O concreto é um material heterogêneo e poroso, sujeito a alterações físicas e químicas quando exposto a condições ambientais extremas, como as temperaturas elevadas. Como a reação de hidratação do cimento é reversível e termo-ativada, a exposição do concreto a temperaturas elevadas pode ter efeitos deletérios, com a ocorrência de desidratação da matriz a base de cimento, fissuração devido a pressões internas geradas pela evaporação da água de amassamento remanescente da mistura e ao desplacamento superficial (spalling). A exposição a temperaturas elevadas pode ocorrer, basicamente em duas situações bastante distintas: _ causas acidentais, como em incêndios, onde os gradientes de temperatura são muito altos e a exposição ao fogo se dá por um período de tempo relativamente curto; _ em condições normais de serviço, como os repositórios de rejeitos radioativos em que a estrutura fica sujeita a temperaturas muito elevadas, por longos períodos de tempo (décadas) . Em um trabalho anterior - FERREIRA (2011, [1]) -, desenvolvido no PGMC em colaboração com a Universidade de Cergy-Pontoise, foi realizada a modelagem termo-hídrico do comportamento de estruturas compostas por camadas de rocha e concreto, semelhantes ao que se encontra em túneis, elementos de instalações hidrelétricas e repositórios destinados a rejeitos nucleares. Foi, então, empregado o código computacional livre CAST3M 2000, desenvolvido no CEA (Commissariat à l'Energie Atomique, França), que é baseado nos conceitos de operadores e objetos e, para validação, foram usados resultados experimentais e numéricos. Propõe-se aqui a incorporação naquele modelo do acoplamento mecânico, através do modelo de dano de Mazars. Tal modelo é válido para situações de carregamento continuamente crescente tem como hipóteses básicas: _ O dano local resulta de deformações de alongamento evidenciadas por sinais positivos de, ao menos, um dos componentes principais de deformação; _ O dano é representado por uma variável escalar D (entre 0 e 1) cuja evolução ocorre quando o valor de alongamento equivalente excede o valor da deformação de referência. A análise dos resultados se baseia na comparação com os resultados obtidos por FERREIRA (2011, [1]) e com os dados experimentais disponíveis para os corpos-de-prova em bicamada rocha-concreto. Nota-se uma clara correspondência numérico/experimental. Discrepâncias observadas indicam a necessidade de estudos mais aprofundados acerca do efeito da degradação mecânica sobre as propriedades térmicas do concreto. / Concrete is a heterogeneous porous material subjected to physical and chemical alterations when exposed to extreme environmental conditions, such as elevated temperatures. Cement paste dehydration may lead to cracking - and even to the ocorrence of spalling - due to internal pressures generated by water vapour formation. The exposure to high temperatures may occur in two different situations: _ accidental causes, as fires, when the temperature gradients are rather elevated and fire exposure takes a relatively short period of time; _ ordinary service conditions, like repositories for radioactive wastes. A previous M.Sc. work developed in the PGMC by FERREIRA (2011, [1]), as part of a scientific cooperation with the University of Cergy Pontoise, dealt with the thermo-hydric modelling of structures composed of concrete-rock bilayers - so as to represent elements present in tunnels, hydroeletric powerplant instalations, for instance. That work employed the free code Cast3M 2000 (developed in the CEA, Commissariat à l'Energie Atomique, França), based on the concepts of operators and objects. Experimental and numerical data were employed for validation. The present work proposes the incorporation of the mechanical coupling to that TH model, through the Mazars Damage Model - with the following basic assumptions: _ Local damage results from elongation deformations; _ Damage is represented by a scalar quantity D. The numerical results are compared with data from FERREIRA (2011, [1]) and experimental information available for concrete-rock bilayer samples. It is observed a clear numerical/experimental correspondence. Resulting discrepancies indicate the need for further investigation concerning the effects of mechanical degradation on the thermical and mechanical properties of concrete.

Orientador: Elias Basile Tambourgi / Tese (doutorado) - Universiade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-20T13:24:06Z (GMT). No. of bitstreams: 1 Moraes_MarleneSilvade_D.pdf: 18744401 bytes, checksum: 214df2eb889315d588ba4e56ffbbc454 (MD5) Previous issue date: 2012 / Resumo: O deslocamento de polímeros, cereais, minérios, produtos farmacêuticos e outros materiais particulados no interior de tubulações, tendo como fluido transportador o ar, é denominado de transporte pneumático. Esta técnica é comumente dividida em transporte em fase densa, com concentração de partículas acima de 30% em volume e transporte em fase diluída, com concentração inferior a 1%. A fase diluída, que não exige tubulações espessas e é de menor custo de aquisição, operação e manutenção, tem como principais inconvenientes: a) o desgaste da parte inferior do tubo transportador devido à má distribuição das partículas na seção transversal; b) a falta de dados da perda de carga de tê com saída de lado, que tem substituído curvas em unidades catalíticas de petróleo por criar um colchão amortecedor e reduzir o desgaste e c) a escassez de informações da relação entre a distribuição de partículas na seção transversal do duto e a perda de carga. O presente trabalho teve como objetivo geral projetar e montar uma unidade experimental, em escala piloto com duto de 117 mm de diâmetro, de transporte pneumático para estudar, em fase diluída, as perdas de carga no trecho vertical, singularidades e a distribuição de partículas na seção transversal. Visou como objetivos específicos: a) construir as curvas de perda de carga em função da velocidade do ar, tendo como parâmetro, as vazões de pellets de polipropileno; b) determinar o valor do coeficiente K, multiplicador da carga cinética da expressão geral de perda de carga localizada para tê com saída de lado, com três prolongamentos (balisas) distintos de 30, 60 e 90 mm e c) obter a distribuição das partículas na seção transversal do duto vertical. A unidade projetada e montada consistiu basicamente de um ventilador centrífugo, com pás semi abertas de 210 mm de diâmetro, acoplado a um motor de rotação variável de 1 cv, um tubo de Pitot horizontal e um vertical, uma válvula rotativa acionada por motor de rotação variável na base de um silo de alimentação, dutos de acrílico estrudados, com diâmetro interno de 117 mm, um sistema de coleta com nove dutos, de seção quadrada paralelos, para análise da distribuição das partículas na seção transversal dos dutos horizontal e vertical e um ciclone. A perda de carga foi determinada através de tomadas de pressão estática, acopladas a anéis piezométricos, com leitura simultânea de todas as tomadas de pressão em uma série de tubos em "U". A velocidade do ar foi obtida por Pitot e anemômetros. A vazão volumétrica do ar foi calculada pelo método das centróides de áreas iguais, com as medidas dos valores coletados pelo Pitot e anemômetro. As vazões dos sólidos particulados foram quantificadas pelo número de revoluções por unidade de tempo da válvula rotativa, aferida pela técnica da massa por tempo. A distribuição de partículas, na seção transversal dos tubos vertical e horizontal e após o tê com saída de lado, foi verificada por pesagem dos sólidos nos coletores. O trabalho forneceu, para o duto horizontal, curvas da perda de carga em função de cinco velocidades de ar de 13,45; 15,18; 16,90; 18,97 e 21,39 m/s e vazões de polipropileno de 0,08; 0,143 e 0,233 kg/s, com a distribuição de partículas em pontos de relevância para projeto. O tê com saída de lado forneceu um coeficiente K de 1,40; com prolongamento de 30 mm, um K de 1,58; com o de 60 mm, um K de 1,43 e com o de 90 mm, um multiplicador (K) igual a 1,47 / Abstract: The displacement of polymers, pharmaceutical cereals, ores, pharmaceutical products and other particulate materials in the interior of tubing , having as fluid transporter the air, is called pneumatic transport. This technique is commonly divided in: transport in dense phase, with particles concentration above 30% in volume and transport in diluted phase, with inferior concentration at 1%. The diluted phase, that does not demand thick tubing and is acquired at lesser cost operation and maintenance, has as main inconveniences: a) the consuming of the inferior part of the transporting pipe due to bad distribution of particles in the transversal session; b) the lack of data of the loss of load of T with side exit, that has been replacing curves in catalytic units of oil for creating a cushioning mattress and reducing consuming and c) the scarcity of information of the relation between the particle distribution in the transversal section of the duct and the loading loss. The present work had as general objective to project and build up an experimental unit, in scale pilot with a 117 mm diameter duct, of pneumatic transport to study, in diluted phase, the losses of load in the vertical stretch, the particle singularities and distribution in the transversal section. It aimed as specific objective: a) to construct the curves of loss of load in function of the air speed, having as parameter, the outflows of pellets of polypropylene; b) to determine the value of coefficient K, multiplier of the kinetic load of the general expression of loss of located load for T with side exit, with three distinct prolongations (boundary-makers): 30, 60 and 90 mm and c) to get the distribution of particles in the transversal section of the vertical duct. The projected and built unit consisted basically on a centrifugal fan, with opened half 210 mm diameter shovels, connected to a 1cv changeable rotation engine, a pipe of horizontal Pitot and one vertical line, a rotating valve set in motion by engine of changeable rotation in the base of a feeding silo, extruded acrylic ducts, with internal diameter of 117 mm, a system of collection with nine ducts, square shaped section parallel, for analysis of the distribution of particles in the transversal section of the horizontal and vertical ducts and a cyclone. The loss of load was determined through static pressure heads, connected to piezometric surface rings, with simultaneous reading of all the pressure heads in a series of pipes in "U". The air speed was gotten by Pitot and anemometers. The volumetric outflow of air was calculated by the method of the centroids of equal areas, with the measures of the values collected by the Pitot and anemometer. The outflows of particulates solids were quantified by the number of revolutions per unit of time of the rotating valve, surveyed by the technique of the mass per time. The particle distribution, in the transversal section of the vertical and horizontal pipes and after T with side exit, was verified by weighing solids in the collectors. The work provided to, the horizontal duct, curves of the loss of load in function of five air speeds of 13,45; 15,18; 16,90; 18,97 and 21,39 m/s and polypropylene outflows of 0,08; 0,143 and 0,233 kg/s, with the particle distribution in points of relevance for project. The T with side exit, provided a 1,40 coefficient K; with a 30mm prolongation, a 1,58 K; with 60 mm, a K of 1,43 and with 90 mm, a multiplier (K) equals to 1,47 / Doutorado / Sistemas de Processos Quimicos e Informatica / Doutora em Engenharia Quimica

Abstract Argon-oxygen decarburisation (AOD) is the most common unit process for refining stainless steel. The AOD process consists of multiple stages, in which the rate of processing is determined by complex reaction mechanisms. The main objective of this work was to study the chemical rate phenomena in selected process stages. For this purpose, an extensive literature review was conducted to clarify the main assumptions of the existing reaction models. Based on the literature review, a new categorisation of the models was proposed. In addition, a literature review was conducted to identify the main phenomena that affect the reaction kinetics in the AOD process. In this work, based on the law of mass action, a novel kinetic approach and its application for modelling of parallel mass transfer controlled reactions were studied. The developed approach enables the simultaneous solution of the chemical equilibrium and mass transfer rate which controls it. A simplified reaction model was employed for studying the effect of mass transfer rates and residual affinity on the constrained equilibrium at the reaction interface. An earlier-proposed AOD model was extended with two phenomenon-based sub-models. The top-blowing model is based on the assumption that reactions take place simultaneously at the surface of the cavity formed by the momentum of the gas jet and on the surface of the metal droplets caused by the shear force of the gas jet. The reduction model describes the reactions during the reduction stage of the AOD process by assuming that all reactions take place between the metal bath and emulsified slag droplets. The results obtained with the models were in good agreement with the measurement data collected from a steel plant. Owing to their phenomenon-based structure, the developed models are well-suited for the analysis of both existing and new production practices. / Tiivistelmä Argon-happimellotus (AOD) on yleisin ruostumattoman teräksen valmistamiseen käytettävä yksikköprosessi. AOD-prosessi koostuu useista vaiheista, joissa prosessointinopeutta määrittävät monimutkaiset reaktiomekanismit. Tutkimuksen päätavoitteena oli tutkia kemiallisia nopeusilmiöitä valituissa prosessivaiheissa. Tähän liittyen tehtiin kattava kirjallisuuskatsaus, jonka tavoitteena oli tunnistaa olemassa olevien reaktiomallien pääoletukset. Kirjallisuuskatsauksen pohjalta esitettiin uusi mallien kategorisointi. Lisäksi tehtiin kirjallisuuskatsaus, jonka tavoitteena oli tunnistaa tärkeimmät reaktiokinetiikkaan vaikuttavat ilmiöt AOD-prosessissa. Tässä työssä tutkittiin uudenlaista massavaikutuksen lakiin perustuvaa lähestymistapaa sekä sen soveltamista rinnakkaisten aineensiirron rajoittamien reaktioiden mallinnukseen. Kehitetty lähestymistapa mahdollistaa kemiallisen tasapainotilan sekä sitä rajoittavan aineensiirron samanaikaisen ratkaisun. Aineensiirtonopeuksien ja jäännösaffiniteetin vaikutusta reaktiopinnalla vallitsevaan rajoitettuun tasapainotilaan tutkittiin käyttämällä yksinkertaistettua reaktiomallia. Aiemmin kehitettyä AOD-mallia laajennettiin kahdella ilmiöpohjaisella alimallilla. Lanssipuhallusmalli perustuu oletukseen, että reaktiot tapahtuvat samanaikaisesti kaasusuihkun liikemäärän muodostaman tunkeuman ja kaasusuihkun leikkausvoiman aiheuttamien metallipisaroiden pinnalla. Pelkistysmalli kuvaa AOD-prosessin pelkistysvaiheen aikana tapahtuvia reaktioita olettaen, että kaikki reaktiot tapahtuvat terässulan ja emulgoituneiden kuonapisaroiden välillä. Malleilla saadut tulokset vastasivat hyvin terästehtaalta kerättyä mittausaineistoa. Ilmiöpohjaisen rakenteensa ansiosta kehitetyt mallit soveltuvat hyvin sekä olemassa olevien että uusien tuotantopraktiikoiden analysoimiseen.

Selectively permeable biological membranes composed of lipophilic barriers inspire the design of biomimetic carrier-mediated membranes for aqueous solute separation. This work imparts selective permeability to lipid-filled pores of silica thin film composite membranes using carrier molecules that reside in the lipophilic self-assemblies. The lipids confined inside the pores of silica are proven to be a more effective barrier than bilayers formed on the porous surface through vesicle fusion, which is critical for quantifying the function of an immobilized carrier. The ability of a lipophilic carrier embedded in the lipid bilayer to reversibly bind the target solute and transport it through the membrane is demonstrated. Through the functionalization of the silica surface with enzymes, enzymatic catalysis and biomimetic separations can be combined on this nanostructured composite platform. The successful development of biomimetic nanocomposite membrane can provide for efficient dilute aqueous solute upgrading or separations using engineered carrier/catalyst/support systems. While the carrier-mediated biomimetic membranes hold great potential, fully understanding of the transport processes in composite synthetic membranes is essential for improve the membrane performance. Electrochemical impedance spectroscopy (EIS) technique is demonstrated to be a useful tool for characterizing the thin film pore accessibility. Furthermore, the effect of lipid bilayer preparation methods on the silica thin film (in the form of pore enveloping, pore filling) on ion transport is explored, as a lipid bilayer with high electrically insulation is essential for detecting activity of proteins or biomimetic carriers in the bilayer. This study provides insights for making better barriers on mesoporous support for carrier-mediated membrane separation process. Porous silica nanoparticles (pSNPs) with pore sizes appropriate for biomolecule loading are potential for encapsulating dsRNA within the pores to achieve effective delivery of dsRNA to insects for RNA interference (RNAi). The mobility of dsRNA in the nanopores of the pSNPs is expected to have a functional effect on delivery of dsRNA to insects. The importance of pores to a mobile dsRNA network is demonstrated by the lack of measurable mobility for both lengths of RNA on nonporous materials. In addition, when the dsRNA could not penetrate the pores, dsRNA mobility is also not measurable at the surface of the particle. Thus, the pores seem to serve as a “sink” in providing a mobile network of dsRNA on the surface of the particle. This work successfully demonstrates the loading of RNA on functionalized pSNPs and identified factors that affects RNA loading and releasing, which provides basis for the delivery of RNA-loaded silica particles in vivo.

One of the most promising routes to renewable liquid fuels and chemicals is the fermentation of waste carbon by specialized microbes. Commercial development of gas fermentation technology is underway but many fundamental research problems must be addressed to further advance the technology towards economic competitiveness. This thesis addresses the important problem of developing integrated metabolic and transport models that predict gas fermentation performance in industrially relevant bubble column reactors. The computational models describe the conversion of CO-rich waste streams including synthesis gas to the platform chemical butyrate. The proposed modeling approach involves combining genome-scale reconstructions of bacterial species metabolism with transport equations that govern the relevant multiphase convective and diffusional processes within the spatially-varying system. I compared the combination of the acetogen Clostridium autoethanogenum for CO conversion to the intermediate acetate and three different gut bacteria (Clostridium hylemonae, Eubacterium rectale and Roseburia hominis) for conversion of acetate to butyrate. Trial-and-error optimization of the three co-culture designs was performed to assess their relative performance and guide future experimental studies.

<div>In many natural and industrial processes, bubbles are exposed to surface-active contaminants (surfactants) that may cover the whole or part of the bubble interface. A partial coverage of the bubble interface results in a spontaneous self-propulsion mechanism, which is yet poorly understood.</div><div>The main goal of this study is to enhance the understanding of the flow and interfacial mechanisms underlying the self-propulsion of small surfactant contaminated bubbles. The focus is on characterizing the self-propulsion regimes generated by the presence of surface-active species, and the influence of surfactant activity and surface coverage on the active bubble motion. </div><div>The study was developed by simultaneously solving the full system of partial differential equations governing the free-surface flow physics and the surfactant transport on the deforming bubble interface using multi-scale numerical simulation. </div><div>Results show in microscopic detail how surface tension gradients (Marangoni stresses) induced by the uneven interfacial coverage produce spontaneous hydrodynamics flows (Marangoni flows) on the surrounding liquid, leading to bubble motion. Results also establish the influence of both surfactant activity and interfacial coverage on total displacement and average bubble velocity at the macroscale. </div><div>Findings from this research improve the fundamental understanding of the free-surface dynamics of self-propulsion and the associated transport of surface-active species, which are critical to important natural and technological processes, ranging from the Marangoni propulsion of microorganisms to the active motion of bubbles and droplets in microfluidic devices. Overall, the findings advance our understanding of active matter behavior; that is, the behavior of material systems with members able to transduce surface energy and mass transport into active movement.</div>