Proper distribution of blood flow in the microcirculation is necessary to match changing oxygen demands in various tissues. How this coordination of perfusion and consumption occurs in heterogeneous microvascular networks remains incompletely understood. Theoretical models are powerful tools that can help bridge this knowledge gap by simulating a range of conditions difficult to obtain experimentally. Here, an algorithm is first developed to estimate blood flow rates in large microvascular networks. Then, a theoretical model is presented for metabolic blood flow regulation in a realistic heterogeneous network structure, derived from experimental results from hamster cremaster muscle in control and dilated states. The model is based on modulation of arteriolar diameters according to the length-tension characteristics of vascular smooth muscle. Responses of smooth muscle cell tone to myogenic, shear-dependent, and metabolic stimuli are included. Blood flow is simulated including unequal hematocrit partition at diverging vessel bifurcations. Convective and diffusive oxygen transport in the network is simulated, and oxygen-dependent metabolic signals are assumed to be conducted upstream from distal vessels to arterioles. Simulations are carried out over a range of tissue oxygen demand. With increasing demand, arterioles dilate, blood flow increases, and the numbers of flowing arterioles and capillaries, as defined by red-blood-cell flux above a small threshold value, increase. Unequal hematocrit partition at diverging bifurcations contributes to capillary recruitment and enhances tissue oxygenation. The results imply that microvessel recruitment can occur as a consequence of local control of arteriolar tone. The effectiveness of red-blood-cell-dependent and independent mechanisms for the metabolic response of local blood flow regulation is examined over a range of tissue oxygen demands. Model results suggest that although a red-blood-cell-independent mechanism is most effective in increasing flow and preventing hypoxia, the addition of a red-blood-cell-dependent mechanism leads to a higher median tissue oxygen level, indicating distinct roles for the two mechanisms. In summary, flow rates in large microvessel networks can be estimated with the proposed algorithm, and the theoretical model for flow regulation predicts a mechanism for capillary recruitment, as well as roles for red-blood-cell-dependent and independent mechanisms in the metabolic regulation of blood flow in heterogeneous microvascular networks.

Ceramics oxides with mixed ionic and electronic conductivity have received a lot of attention due to their wide range of applications in solid oxide fuel cells, interconnects, gas sensors, and ion transport membranes. However, owing to harsh operating conditions, the choice of proper materials and engineering their properties are still challenging. Perovskite and fluorite structures are two promising structures for ceramic membrane applications. The objective of this research is to explore the stability of lanthanum chromite-based perovskite ((La,Sr)(Cr,Fe)O3-δ) as single phases and dual-phase composites with fluorite phases under fabrication and operating conditions of Oxygen Transport Membranes (OTM). The current research has been categorized into two sections: structural and chemical stability of perovskite phases and dual-phase perovskite/fluorite composites. Also, investigation on both categories has been conducted with two separate approaches: experimental examinations and computational Thermodynamic. In the computational part, independent methods have been considered for the single-phase perovskite and dual-phase perovskite/fluorite composites. In the experimental section, the bulk chemical stability of the dual-phase samples has been examined under controlled oxygen partial pressure p(O2) atmospheres at 1400ᵒC for 10 hours with slow and fast cooling rates. Besides, the phase stability of the perovskite structures as a single-phase has been also examined under OTM fabrication conditions. The results present new phenomena in the chemical stabilities of the materials. They include formations of liquid phases, Sr-segregation, and perovskite phase separations. The correlations between compositions/ temperature/ p(O2) and secondary phases have been investigated to improve the chemical stability and extend the lifetime of the materials. The findings in this thesis enhance the knowledge about the chemical stabilities of OTMs and help to develop more reliable materials for ceramic-based OTMs.

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Ceramics oxides with mixed ionic and electronic conductivity have received a lot of attention due to their wide range of applications in solid oxide fuel cells, interconnects, gas sensors, and ion transport membranes. However, owing to harsh operating conditions, the choice of proper materials and engineering their properties are still challenging. Perovskite and fluorite structures are two promising structures for ceramic membrane applications. The objective of this research is to explore the stability of lanthanum chromite-based perovskite ((La,Sr)(Cr,Fe)O3-δ) as single phases and dual-phase composites with fluorite phases under fabrication and operating conditions of Oxygen Transport Membranes (OTM). The current research has been categorized into two sections: structural and chemical stability of perovskite phases and dual-phase perovskite/fluorite composites. Also, investigation on both categories has been conducted with two separate approaches: experimental examinations and computational Thermodynamic. In the computational part, independent methods have been considered for the single-phase perovskite and dual-phase perovskite/fluorite composites. In the experimental section, the bulk chemical stability of the dual-phase samples has been examined under controlled oxygen partial pressure p(O2) atmospheres at 1400ᵒC for 10 hours with slow and fast cooling rates. Besides, the phase stability of the perovskite structures as a single-phase has been also examined under OTM fabrication conditions. The results present new phenomena in the chemical stabilities of the materials. They include formations of liquid phases, Sr-segregation, and perovskite phase separations. The correlations between compositions/ temperature/ p(O2) and secondary phases have been investigated to improve the chemical stability and extend the lifetime of the materials. The findings in this thesis enhance the knowledge about the chemical stabilities of OTMs and help to develop more reliable materials for ceramic-based OTMs.

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[ES] Esta tesis está centrada en la combinación de diferentes tecnologías para mejorar las tecnologías emergentes de captura y almacenamiento de carbono (CSS) y la revalorización del CO2 capturado. La principal tecnología estudiada en esta tesis fueron las membranas de transporte de oxigeno (OTMs), las cuales pueden producir oxigeno puro de forma más flexible que las actuales tecnologías de producción de oxigeno, como la destilación criogénica de aire. La producción de oxigeno puro es crucial para desarrollar reactores de oxicombustión que podrían ser mas eficientes para la captura de CO2 que los reactores actuales de combustión con aire. Los estudios sobre OTMs se dividieron en dos temas principales: membranas de bifásicas estables en CO2 y membranas basadas en BSCF (Ba1-xSrxCo1-yFeyO3-¿). Por otro lado, para la revalorización del CO2 capturado, se estudio' la tecnología de looping químico basada en catalizador de oxido de cerio, que aprovecha las propiedades redox del catalizador a diferentes pO2 y altas temperaturas (entre 700- 1400 ¿C). En general, las principales etapas limitantes en OTMs son la transferencia de oxigeno a trave's de la membrana y las reacciones superficiales. Por eso, una mejora en las propiedades de la capa catalítica podri'a mejorar la permeacio'n total de oxigeno. El primer estudio sobre membranas bifásicas se centro' el estudio de capas catali'ticas con distintas proporciones de ambas fases. Para este estudio, se selecciono' el NFO-CTO (NiFe2O4/Ce0.8Tb0.2O2-¿) como composite. Este material ya ha sido estudiado en nuestro laboratorio, y mostró una gran estabilidad en atmósferas de CO2, pero con baja permeación de O2 en comparación con otros composites. Este estudio mostró resultados interesantes, y se combino' con medidas de espectroscopia de impedancia electroqui'mica (EIS), utilizadas habitualmente para estudiar electrodos para pilas de combustible de o'xido so'lido (SOFC) y pilas de electro'lisis de o'xido so'lido (SOEC). El segundo estudio sobre composites para OTMs se centro' en el aumento de la permeacio'n de oxi'geno con composites basados en espinela-fluorita. En este caso, el transporte de oxigeno esta' controlado, adema's de por la temperatura y el gradiente de pO2, por la conductividad ambipolar, en la que intervienen las conductividades eléctrica e io'nica. Asi', se cambio' la fase de NFO por la fase de CMO (Co2MnO4) que tiene mayor conductividad total que el NFO. El composite resultante (CMO-CTO) ha mostrado un mayor rendimiento que el material predecesor NFO-CTO. Como se ha mencionado anteriormente, el otro estudio sobre OTM se realizo' con membranas basadas en BSCF. En este estudio, la membrana capilar BSCF fue electrificada para aumentar la temperatura de la membrana por efecto Joule y como consecuencia un aumento en la permeación de oxigeno. Además, se estudió este efecto bajo deshidrogenacio'n oxidativa de etano, obteniéndose una mejora importante para las membranas BSCF electrificadas en comparación con las membranas BSCF no electrificadas. Estos estudios abren las puertas al uso de ellas con reactores a más baja temperatura. El último estudio se centra en la revalorización del CO2 mediante el reformado de metano por ciclos químicos. Los ciclos químicos están basados en las propiedades redox del catalizador y las dos etapas de reducción y oxidación del catalizador. La reducción del catalizador es realizada mediante temperatura y en condiciones inertes o con corrientes reductoras como por ejemplo en metano. Los estudios se centran en la reducción a través de metano que trabaja a temperaturas más bajas que para corrientes inertes y, ademas, proporciona corrientes de syngas (mezcla de CO y H2) en la etapa de reducción del catalizador, que mejora la eficiencia global del proceso. La revalorización del CO2 se realizaba en la etapa de oxidación del catalizador. La oxidación de estos catalizadores podría formarse con flujos de H2O y/o / [CA] Aquesta tesi està centrada en la combinació de diferents tecnologies per millorar les tecnologies emergents de captura i emmagatzematge de carboni (CSS) i la revalorització del CO2 capturat. La principal tecnologia estudiada en aquesta tesi van ser les membranes de transport d'oxigen (OTMs), les quals poden produir oxigen pur de manera més flexible que les actuals tecnologies de producció d'oxigen, com la destil·lació criogènica de l'aire. La producció d'oxigen pur és crucial per al desenvolupament de reactors d'oxicombustió que podrien ser més eficients per a la captura de CO2 que els reactors actuals de combustió amb aire. Els estudis sobre OTMs es van dividir en dos temes principals: membranes composites de dos fases estables en CO2 i membranes basades en BSCF (Ba1- xSrxCo1-yFeyO3-). D'altra banda, per a la revalorització del CO2 capturat, es va estudiar la tecnologia de looping químic basada en catalitzador d'òxid de ceri, que aprofita les propietats redox del catalitzador a diferents pO2 i altes temperatures (entre 700-1400 ºC). En general, les principals etapes limitants en OTMs són la transferència d'oxigen a través de la membrana i les reaccions superficials. Per això, una millora en les propietats de la capa catalítica podria millorar la permeació total d'oxigen. El primer estudi sobre membranes bifàsiques es va centrar en l'estudi de capes catalítiques amb diferents proporcions de ambdues fases. Per a aquest estudi, es va seleccionar el NFO-CTO (NiFe2O4/Ce0.8Tb0.2O2-δ) com a composite. Aquest material ja ha sigut estudiat en el nostre laboratori, i va mostrar una gran estabilitat en atmosferes de CO2, però amb baixa permeació d'O2 en comparació amb altres composites. Aquest estudi va mostrar resultats interessants, i es va combinar amb mesures d'espectroscòpia d'impedància electroquímica (EIS), utilitzades habitualment per estudiar elèctrodes per a piles de combustible d'òxid sòlid (SOFC) i piles d'electròlisi d'òxid sòlid (SOEC). El segon estudi sobre composites per a OTMs es va centrar en l'augment de la permeació d'oxigen amb composites basats en espinela-fluorita. En aquest cas, el transport d'oxigen està controlat, a més de per la temperatura i el gradient de pO2, per la conductivitat ambipolar, en la qual intervenen les conductivitats elèctrica i iònica. Així, es va canviar la fase de NFO per la fase de CMO (Co2MnO4) que té una major conductivitat total que el NFO. El composite resultant (CMO-CTO) ha mostrat un major rendiment que el material predecessor NFO-CTO. L'últim estudi es centra en la revalorització del CO2 mitjançant el reformat de metà per cicles químics. Els cicles químics estan basats en les propietats redox del catalitzador i les dues etapes de reducció i oxidació del catalitzador. La reducció del catalitzador és realitzada mitjançant temperatura i en condicions inertes o amb corrents reductores com per exemple en metà. Els estudis se centren en la reducció a través de metà que treballa a temperatures més baixes que per a corrents inertes i, a més, proporciona corrents de syngas (barreja de CO i H2) en l'etapa de reducció del catalitzador, que millora l'eficiència global del procés. La revalorització del CO2 es realitzava en l'etapa d'oxidació del catalitzador. L'oxidació d'aquests catalitzadors podria formar-se amb fluxos de H2O i/o CO2 a altes temperatures 700- 1000 ºC. El nostre estudi es centra en òxids de ceri dopats al 10% amb elements 19Chapter 0: Preamble trivalent, generalment lantànids. En aquest estudi es va correlacionar la velocitat de splitting del CO2 en l'etapa d'oxidació amb el volum de cel·la de l'estructura cristal·lina i la conductivitat total d'aquests materials. / [EN] This thesis is focused on the combination of different technologies to improve emerging technologies for carbon capture and storage (CSS) and the revalorization of the CO2 captured. The leading technology studied in this thesis was oxygen transport membranes (OTMs) that could produce pure oxygen more flexibly than the current oxygen production technologies like cryogenic air distillation. The production of pure oxygen is crucial for developing oxycombustion reactors that could be more efficient for carbon capture than traditional combustion reactors. The OTMs studies were divided into two main topics: dual-phase membranes with stable operation in CO2 and BSCF-based membranes (Ba1-xSrxCo1-yFeyO3-¿). For the revalorization of the captured CO2, the chemical looping technology based on a cerium oxide catalyst was studied, which takes advantage of the redox properties of the catalyst at different pO2 and high temperatures (between 700-1400 ¿C). In general, the principal limiting steps for OTMs were the bulk oxygen transfer and the surface exchange reactions. In this matter, the improvement in the behaviour of the catalytic layer could achieve better oxygen permeation. The first study for dual- phase membranes was focused on the role of the different dual-phase ratios in the behaviour as a catalytic layer in OTMs. For this study, NFO-CTO (NiFe2O4/Ce0.8Tb0.2O2-¿) was selected as dual-phase material. This material was previously studied and showed high stability under CO2 environments but with poor oxygen flux compared with other dual-phase materials. The study considered for the present Thesis showed interesting results, and it was combined with electrochemical impedance spectroscopy (EIS) measurements, commonly used to study electrodes for solid oxide fuel cells (SOFC) and solid oxide electrolysis cells (SOEC). The second study in dual-phase materials for OTMs focused on the increase in oxygen permeation for spinel-fluorite-based materials. In this matter, the bulk oxygen transports are controlled, apart from the temperature and the pO2 gradient, by the ambipolar conductivity, where the electrical and the ionic conductivities are involved. So, the NFO phase was changed for the CMO phase (Co2MnO4), which has higher total conductivity than the NFO. The resultant dual- phase material (CMO-CTO) performed better than the predecessor NFO-CTO material. As mentioned previously, the other study on OTMs focused on BSCF-based membranes. In this study, the BSCF capillary membrane was electrified in order to increase the membrane temperature via the Joule effect and, as a consequence, an increase in the oxygen permeation. In addition, this effect under oxidative dehydrogenation of ethane was studied, obtaining an essential improvement for electrified BSCF membranes compared with non-electrified BSCF membranes. These studies have opened new gates to operate these membranes at lower reactor temperatures. Finally, the last study was focused on CO2 upcycling via chemical looping methane reforming. Chemical looping is based on the redox properties of the catalyst in two principal steps, reduction and oxidation of the catalyst. The catalyst reduction is performed with temperature in inert conditions or with reducing streams like methane. We were focused on the reduction via methane that works at lower temperatures than inert streams and could provide syngas streams (a mixture of CO and H2) that improve global efficiency. The revalorization of the CO2 was performed in the other step, the oxidation part of the cycle. The oxidation of those catalysts could be formed with H2O and/or CO2 streams at high temperatures of 700-1000 ¿C. Our study was focused on 10% doped cerium oxide with trivalent elements. In this study, the CO2 splitting on the oxidation step was correlated with the crystal structure parameters and the total conductivity of these materials. / Laqdiem Marín, M. (2024). Development of high temperature MIEC catalytic reactors for energy conversion and storage aplications [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/204871