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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
121

Étalements de fluides à seuil / Coatings of yield stress fluids

Maillard, Mathilde 28 September 2015 (has links)
Les fluides à seuil sont des matériaux utilisés dans de nombreux procédés industriels au cours desquels ils sont mis en écoulement via leur interaction avec des outils solides. Afin de mieux comprendre comment ils s'étalent sur des surfaces, nous avons étudié d'une part leur enduction verticale sur une plaque mince et d'autre part leur étalement horizontal à l'aide d'une lame. Ces deux études se sont appuyées sur des mesures macroscopiques permettant de suivre la force appliquée à l'outil et des mesures microscopiques de PIV pour déterminer les champs de vitesse dans le matériau. Après confirmation de leur validité par comparaison avec nos résultats expérimentaux, des simulations numériques basées sur la programmation conique ont permis de préciser les écoulements en jeu. Pour l'enduction par trempage, nous observons que dans notre gamme d'étude, le dépôt de fluide à seuil sur la plaque est millimétrique et d'épaisseur constante, sauf aux extrémités. Selon le rapport des forces visqueuses et plastiques, l'enduction est régie par un équilibre "seuillo-gravitaire" ou "visco-gravitaire". Nous avons ensuite caractérisé l'écoulement généré dans le bain par le déplacement de la plaque afin d'expliciter l'origine du phénomène d'enduction. Les simulations numériques précisent la forme de cet écoulement. L'étalement horizontal dans un canal à l'aide d'une lame mince conduit au déplacement d'un amas de fluide faiblement cisaillé par rapport à une région de fluide au repos, par l'intermédiaire d'une couche cisaillée. Nous montrons qu'un modèle simple permet de prédire la dynamique de croissance de l'amas et la relie à la force normale à la lame / Yield stress fluids are used in various industrial processes in which solid tools make them flow. To have a better understanding on how they spread on surfaces, we first studied the vertical coating on a thin plate and then the horizontal blade-coating. Both studies are based on macroscopic measures recording the force applied on the plate and on the microscopic determination on the velocity fields in the fluid by PIV. Numerical simulations based on cone programming, which validity had been confirmed in comparison to our experimental results, specified the flows at stake. In dip-coating, we observed than within our framework, the yield stress fluid deposit on the plate is millimetric and of constant thickness, except on the tips. According to the value of the viscous over plastic forces ratio, the coating is led by a "yield-gravity" or a "visco-gravity" balance. Then, we characterized the flow generated in the bath by the plate displacement in order to clarify the origin of the coating phenomenon. The numerical simulations specified the flow characteristics. The horizontal blade-coating in a channel involves the displacement of a weakly sheared cluster of fluid in relation to a part of fluid at rest, through a sheared layer. We showed that the growing dynamic of the cluster is described with a simple model which links it to the normal force to the plate
122

Photoélectrolyse de l'eau : étude de matériaux semiconducteurs de type p comme photocathode pour la réduction de protons en H2 / Water splitting : study of p-type semiconducting materials as photocathode for protons reduction into H2

Toupin, Johanna 09 February 2016 (has links)
L’objectif de ce travail a été d’étudier des matériaux semiconducteurs de type p comme photocathode pour la réduction de protons dans le cadre de la photoélectrolyse de l’eau. Ainsi, deux types de matériaux ont été étudiés, des oxydes de cuivre, Cu2O et CuO, et des matériaux à structure pérovskite (ATiO3, A=Ca, Ba, Sr) dopées au fer et à l’azote. Les oxydes de cuivre ont été synthétisés par deux voies différentes afin d’obtenir des films : par voie sol-gel couplée au dip-coating et par électro-dépôt et anodisation du cuivre. La photocorrosion des oxydes de cuivre en milieu aqueux et sous illumination a été mise en évidence. La protection des oxydes de cuivre via une hétérojonction avec un semiconducteur de type n (TiO2 ou BaTiO3) a révélé une meilleure stabilité des électrodes au cours du temps ainsi que des photocourants élevés grâce à une composition et une architecture originales. Les pérovskites ont été synthétisées par voie sol-gel couplée au dip-coating. Ce sont des semiconducteurs de type n ; ainsi l’étude du dopage au fer, pour substituer le titane, et à l’azote, pour substituer l’oxygène, a mis en évidence un changement de nature de type n à type p, ainsi qu’une diminution de la largeur de bande interdite. Les propriétés physico-chimiques de toutes les électrodes synthétisées ont été caractérisées (structure cristalline, morphologie, propriétés optiques et électrochimiques) et discutées en fonction de leur composition et des paramètres de synthèse. Ces travaux ont permis d’élaborer des photocathodes originales, performantes et stables au cours du temps (oxydes de cuivre protégées), et de démontrer l’utilisation de pérovskites dopées pour cette application. / The aim of this work was to study p-type semiconducting materials as photocathodes for protons reduction into H2 for water splitting application. Two types of materials have been studied: copper oxides, Cu2O and CuO, and materials with a perovskite structure (ATiO3, A=Ca, Ba, Sr) doped by iron and nitrogen. Copper oxides have been synthetized by two different ways in order to obtain films: sol-gel process coupled with dip-coating and copper plating and anodization. Copper oxides photocorrosion has been highlighted in aqueous environment and under illumination. Their protection via a heterojunction with an n-type semiconductor (TiO2 and BaTiO3) improved electrodes stability over time and photocurrents, thanks to original composition and architecture. Perovskites have been synthetized by sol-gel process coupled with dip-coating. They are well-known as n-type semiconductors; so the study of doping with iron, to substitute titanium, and with nitrogen, to substitute oxygen, shows a change from n-type to p-type, and a reduction of the band gap. The physical and chemical properties of the synthetized electrodes were characterized (crystal structure, morphology, optical and photoelectrochemical properties) and discussed according to the composition and synthesis parameters. This work enables to obtain original, efficient, and stable over time, photocathodes (protected copper oxides) and to demonstrate the potential use of doped perovskites for this application.
123

Vliv žárového zinkování na vlastnosti vysokopevnostích ocelí / Influence of hod dip galvanizing on properties of high-strenght steels

Křemen, Jan January 2010 (has links)
This thesis deals with the influence of hod dip galvanizing on properties of high-strenght steel. Galvanizing adversely affects the mechanical properties of high-strenght steel. This paper also examines the influence of hod dip galvanizing at hardness high-strenght steels. The task is to assess how the yield stress can galvanize steel.
124

Quantitative Analysis of Antioxidants from High Density Polyethylene (HDPE) by off-line Supercritical Fluid Extraction Coupled High Performance Liquid Chromatography

Pinto, Angela Marie III 27 August 1997 (has links)
Plastics are widely used and they vary in their applicability, ranging from automobile parts, components for houses and buildings, and packaging for everything from food to electronic parts. The diverse applications of plastics, such as polystyrene, polyolefins and polyester, are credited to the incorporation of additives. Additives improve the performance of these and other polymer resins. Without the incorporation of such additives, for example Ethanox ® 330, some plastics would degrade during processing or over time. To ensure that the specified amount of an additive or combination of additives are incorporated into a polymer after the extrusion process, a rapid and accurate analytical method is required. Quantitation of additive(s) in the polymer is necessary, since the additive(s) may degrade and the amount of additive(s) can influence the physical nature of the polymer. Conventional extraction techniques for polymer additive(s), such as, Soxhlet or dissolution / precipitation are labor intensive, time consuming, expensive, and the optimal recovery is significantly less than 90 percent. In addition, a large amount of solvent , such as toluene or decalin, must be eliminated in order to concentrate the sample prior to chromatographic separation. Supercritical Fluid Extraction (SFE) has been employed as an alternative polymer preparation technique. SFE is a favorable means for various analytical sample preparation applications, credited to its short extraction times. This research employs SFE for the extraction of the antioxidant Ethanox® 330 from high density polyethylene (HDPE) followed by HPLC/UV analysis. The effects of temperature, modifier type, and modifier concentration were investigated. Once the optimal extraction conditions were determined, the extraction efficiency of Ethanox ® 330 as a single additive and in the presence of co-additives from HDPE were investigated. Recoveries of greater than 90% were obtained for Ethanox ® 330 when a secondary antioxidant was present in the HDPE. / Master of Science
125

SHORT-TERM FORMATION KINETICS OF THE CONTINUOUS GALVANIZING INTERFACIAL LAYER ON MN-CONTAINING STEELS

Alibeigi, Samaneh 11 1900 (has links)
Aluminium is usually added to the continuous hot-dip galvanizing bath to improve coating ductility and adhesion through the rapid formation of a thin Fe-Al intermetallic layer at the substrate-liquid interface, thereby inhibiting the formation of brittle Fe-Zn intermetallic compounds. On the other hand, Mn is essential for obtaining the desired microstructure and mechanical properties in advanced high strength steels, but is selectively oxidized in conventional continuous galvanizing line annealing atmospheres. This can deteriorate reactive wetting by the liquid Zn(Al,Fe) alloy during galvanizing and prevent the formation of a well developed Fe-Al interfacial layer at the coating/substrate interface, resulting in poor zinc coating adherence and formability. However, despite Mn selective oxidation and the presence of surface MnO, complete reactive wetting and a well developed Fe-Al interfacial layer have been observed for Mn-containing steels. These observations have been attributed to the aluminothermic reduction of surface MnO in the galvanizing bath. According to this reaction, MnO is reduced by the bath dissolved Al, so the bath can have contact with the substrate and form the desired interfacial layer. Heat treatments compatible with continuous hot-dip galvanizing were performed on four different Mn-containing steels whose compositions contained 0.2-3.0 wt% Mn. It was determined that substrate Mn selectively oxidized to MnO for all alloys and process atmospheres. Little Mn surface segregation was observed for the 0.2Mn steel, as would be expected because of its relatively low Mn content, whereas the 1.4Mn through 3.0Mn steels showed considerable Mn-oxide surface enrichment. In addition, the proportion of the substrate surface covered with MnO and its thickness increased with increasing steel Mn content.A galvanizing simulator equipped with a He jet spot cooler was used to arrest the reaction between the substrate and liquid zinc coating to obtain well-characterized reaction times characteristic of the timescales encountered while the strip is resident in the industrial continuous galvanizing bath and short times after in which the Zn-alloy layer continues to be liquid (i.e. before coating solidification). Two different bath dissolved Al contents (0.20 and 0.30 wt%) were chosen for this study. The 0.20 wt% Al bath was chosen as it is widely used in industrial continuous galvanizing lines. The 0.30 wt% Al bath was chosen to (partially) compensate for any dissolved Al consumption arising from MnO reduction in the galvanizing bath.The Al uptake increased with increasing reaction time following non-parabolic growth kinetics for all experimental steels and dissolved Al baths. For the 0.20 wt% dissolved Al bath, the interfacial layer on the 1.4Mn steel showed the highest Al uptake, with the 0.2Mn, 2.5Mn and 3.0Mn substrates showing significantly lower Al uptake. However, increasing the dissolved bath Al to 0.30 wt% Al resulted in a significantly increased Al uptake being observed for the 2.5Mn and 3.0Mn steels for all reaction times. These observations were explained by the combined effects of the open microstructures associated with the multi-phase nature of an oxide-containing interfacial layer and additional Al consumption through MnO reduction. For instance, in the case of the 1.4Mn steel, the more open interfacial layer structure accelerated Fe diffusion through the interfacial layer and increased Al uptake versus the 0.2Mn substrate for the same bath Al. However, in the case of the 2.5Mn and 3.0Mn substrates and 0.20 wt% Al bath, additional Al consumption through MnO reduction caused the interfacial layer growth to become Al limited, whereas the very open structure dominated growth in the case of the 0.30 wt% Al bath and resulted in the changing the growth kinetics from mixed diffusion-controlled to a more interface controlled growth mode. A kinetic model based on oxide film growth (Smeltzer et al. 1961, Perrow et al. 1968) was developed to describe the Fe-Al interfacial layer growth kinetics within the context of the microstructural evolution of the Fe-Al interfacial layer for Mn-containing steels reacted in 0.20 wt% and 0.30 wt% dissolved Al baths. It indicated that the interfacial layer microstructure development and the presence of MnO at the interfacial layer had significant influence on the effective diffusion coefficient and interfacial layer growth rate. However, in the cases of the 2.5Mn and 3.0Mn steels in 0.20 wt% Al bath, the kinetic model could not predict the interfacial layer Al uptake, since the Fe-Al growth was Al limited. In fact, in these cases, additional Al was consumed for reducing their thicker surface MnO layer, resulted in limiting the dissolved Al available for Fe-Al growth. / Dissertation / Doctor of Science (PhD)
126

Characterization and Biomechanical Analysis of the Human Lumbar Spine with <em>In Vitro</em> Testing Conditions

Stolworthy, Dean K. 19 January 2012 (has links) (PDF)
Biomechanical testing of cadaveric spinal segments forms the basis for our current understanding of healthy, pathological, and surgically treated spinal function. Over the past 40 years there has been a substantial amount of data published based on a spinal biomechanical testing regimen known as the flexibility method. This data has provided valuable clinical insights that have shaped our understanding of low back pain and its treatments. Virtually all previous lumbar spinal flexibility testing has been performed at room temperature, under very low motion rates, without the presence of a compressive follower-load to simulate upper body weight and the action of the musculature. These limitations of previous work hamper the applicability of published spinal biomechanics data, especially as researchers investigate novel ways of treating low back pain that are intended to restore the spine to a healthy biomechanical state. Thus, the purpose of this thesis work was to accurately characterize the rate-dependent flexibility of the lumbar spine at body temperature while in the presence of a compressive follower-load. A custom spine simulator with an integrated environmental chamber was developed and built as part of this thesis work. Cadaveric spinal motion segments were tested at 12 different rates of loading spanning the range of voluntary motion rates. The testing methodology allowed for comparison of spinal flexibility at room and body temperatures in the three primary modes of spinal motion, both with and without a compressive follower-load. Additionally, the work developed a stochastic model for rate-dependent spinal flexibility that allows for accurate prediction of spinal flexibility at any rate within the range of voluntary motion, based on a single flexibility test. In conclusion, the biomechanical response was significantly altered due to testing temperature, loading-rate, and application of a compressive follower-load. The author emphasizes the necessity to simulate the physiological environment during ex vivo biomechanical analysis of the lumbar spine in order to obtain a physiological response. Simplified testing procedures may be implemented only after the particular effect is known.
127

Double Dip – kan ett bolag som finansierat sig via ett koncerninternt finansbolag, som emitterat obligationer, utsättas för dubbla betalningskrav vid bolagets konkurs eller företagsrekonstruktion?

Oxhammar, Vilhelm January 2024 (has links)
No description available.
128

Mechanical Property Development, Selective Oxidation, and Galvanizing of Medium-Mn Third Generation Advanced High Strength Steel

Bhadhon, Kazi Mahmudul Haque 11 1900 (has links)
Medium Mn (med-Mn) third generation advanced high strength steels (3G AHSSs) are promising candidates for meeting automotive weight reduction requirements without compromising passenger safety. However, the thermal processing of these steels should be compatible with continuous galvanizing line (CGL) processing capabilities as it provides cost-effective, robust corrosion protection for autobody parts. Hence, the main objective of this Ph.D. research is to develop a CGL-compatible thermal processing route for a prototype 0.2C-6Mn-1.5Si-0.5Al-0.5Cr-xSn (wt%) (x = 0 and 0.05 wt%) med-Mn steel that will result in the 3G AHSS target mechanical properties (24,000 MPa%  UTS × TE  40,000 MPa%) and high-quality galvanized coatings via enhanced reactive wetting. It was found that the starting microstructure, intercritical annealing (IA) time/temperature, and Sn micro-alloying had a significant effect on the retained austenite volume fraction and stability and, thereby, the mechanical properties of the prototype med-Mn steel. For the as-received cold-rolled (CR) starting microstructure, the intercritical austenite nucleated and grew on dissolving carbide particles and resulted in blocky retained austenite. However, Sn micro-alloying significantly effected the intercritical austenite chemical stability by segregating to the carbide/matrix interface and retarding C partitioning to the intercritical austenite. This resulted in lower volume fractions of low stability retained austenite which transformed to martensite (via the TRIP effect) at low strains, thereby quickly exhausting the TRIP effect and resulting in a failure to sustain high work hardening rates and delay the onset of necking. Consequently, the Sn micro-alloyed CR starting microstructure was unsuccessful in achieving 3G AHSS target mechanical properties regardless of the IA parameters employed. Contrastingly, the CR starting microstructure without Sn micro-alloying was able to meet target 3G mechanical properties via intercritical annealing at 675 °C × 60 s and 120 s, and at 690 °C × 60 s owing to sufficiently rapid carbide dissolution and C/Mn partitioning into the intercritical austenite such that it had sufficient mechanical and chemical stability to sustain a gradual deformation-induced transformation to martensite and maintain high work hardening rates. On the other hand, the martensitic (M) starting microstructure produced higher volume fractions of chemically and mechanically stable lamellar retained austenite regardless of Sn micro-alloying. Intercritical annealing at 650 °C × 60 s and 675 °C × 60 s and 120 s produced 3G AHSS target mechanical properties. It was shown that the stable lamellar retained austenite transformed gradually during deformation. Furthermore, deformation-induced nano-twin formation in the retained austenite was observed, suggesting the TWIP effect being operational alongside the TRIP effect. As a result, a continuous supply of obstacles to dislocation motion was maintained during deformation, which aided in sustaining a high work hardening rate and resulted in a high strength/ductility balance, meeting 3G AHSS target properties. Based on these results, the martensitic starting microstructure without Sn micro-alloying and the M-675 °C × 120 s IA condition were chosen for the selective oxidation and reactive wetting studies. The selective oxidation study determined the effect of a N2-5H2-xH2O (vol%) process atmosphere pO2 (–30, –10, and +5 °C dew point (Tdp)) on the composition, morphology, and spatial distribution of the external and internal oxides formed during the austenitizing and subsequent intercritical annealing cycles. The objective of this study was to identify the process atmosphere for the promising M-675 °C × 120 s heat treatment that would result in a pre-immersion surface that could be successfully galvanized in a conventional galvanizing (GI) bath. The austenitizing heat treatment (775 °C × 600 s) used to produce the martensitic starting microstructure resulted in thick (~ 200 nm) external oxides comprising MnO, MnAl2O4, MnSiO3/Mn2SiO4, and MnCr2O4, regardless of the process atmosphere pO2. However, intermediate flash pickling was successful in dissolving the external oxides to a thickness of approximately 30 nm along with exposing metallic Fe in areas which contained relatively thin external oxides. Furthermore, extruded Fe nodules that were trapped under the external oxides were revealed during the flash pickling process. Overall, flash pickling resulted in a surface consisting of dispersed external oxide particles with exposed metallic substrate and extruded Fe nodules. This external surface remained unchanged during IA owing to the multi-micron (~ 2–8 µm) solute-depleted layer that formed during the austenitizing heat treatment. Subsequent galvanizing in a 0.2 wt% (dissolved) Al GI bath with an immersion time of 4 s at 460 °C was successful in achieving high-quality, adherent galvanized coatings through multiple reactive wetting mechanisms. The dispersed nodule-type external oxides along with exposed substrate and extruded Fe nodules on the pre-immersion surface facilitated direct wetting of the steel substrate and promoted the formation of a robust and continuous Fe2Al5Znx interfacial layer at the steel/coating interface. Additionally, oxide lift-off, oxide wetting, bath metal ingress, and aluminothermic reduction were operational during galvanizing. The galvanized med-Mn steels met 3G AHSS target mechanical properties. Overall, this Ph.D. research showed that it is possible to employ a CGL-compatible thermal processing route for med-Mn steels to successfully produce 3G AHSS target mechanical properties as well as robust galvanized coatings. / Thesis / Doctor of Philosophy (PhD) / One of the largest challenges associated with incorporating the next generation of advanced high strength steels into the automotive industry lies in processing these steels in existing industrial production lines. In that regard, a two-stage heat treatment with an intermediate flash pickling stage and process atmosphere compatible with existing industrial continuous galvanizing line technology was developed for a prototype medium-Mn steel. The heat-treated prototype steel met the target mechanical properties outlined for the next generation of advanced high strength steels. Furthermore, the heat treatment and process atmosphere utilised in this research produced a surface that facilitated the successful galvanizing of the prototype medium-Mn steel. This adherent and high-quality galvanized coating will provide robust corrosion protection if the candidate medium-Mn steel is used in future automotive structural applications.
129

GIS Uses for Modeling Subsurface Conditions in Ohio Coal Mines

Kleski, Kurt W. January 2017 (has links)
No description available.
130

Development of electrocatalytic layers and thermo-fluid dynamic evaluation for high temperature membrane reactors

Catalán Martínez, David 20 January 2020 (has links)
[ES] En la presente tesis se han desarrollados estudios sobre reactores de membrana de alta temperatura. Entre estos se puede diferenciar entre un trabajo experimental y un trabajo de simulación. En el bloque experimental se han desarrollado electrodos basados en cobre para reactores de membrana electroquímicos tubulares de alta temperatura basados en electrolitos protónicos. Para depositar estos electrodos sobre los tubos se han desarrollado diferentes técnicas. Se ha optimizado el método dip-coating para depositar un cermet basado en cobre utilizando la misma cerámica que el electrolito de los soportes tubulares. Las condiciones con las que se llevó a cabo el proceso de dip-coating provocan disminuciones de varios ordenes de magnitud en la resistencia de polarización del electrodo final. Se trata de un método que es muy sensible a posibles defectos en electrolito, como pequeñas grietas o poros, ya que el cobre del electrodo depositado se introduce por estos defectos reaccionando con el níquel del electrodo interno. Asimismo, se ha empleado el método de sputtering para depositar cobre metálico sobre soportes tubulares electroquímicos. Aumentar la temperatura de deposición genera mejores fijaciones electrodo-electrolito. Las celdas con el cobre depositado a alta temperatura mostraron resistencias de polarización inferiores a 0.1 ¿·cm^2. En el bloque de simulaciones mediante métodos de elementos finitos se han desarrollado diferentes modelos para la caracterización de los fenómenos que tienen lugar en reactores de membrana de alta temperatura. Se ha estudiado: (i) la permeación de oxígeno a través de una membrana de conducción iónica-electrónica mixta; (ii) la electrólisis del agua utilizando celdas basadas en conductores protónicos de alta temperatura; (iii) la integración de una celda protónica para la extracción de hidrógeno en un reformador de metano; (iv) la integración de una celda de conductividad co-iónica en la deshidroaromatización de metano en un reactor de lecho catalítico. El modelo de permeación de oxígeno a través de una membrana de conductividad mixta se ajustó a datos experimentales. El modelo ajustado ha permitido caracterizar la importancia del efecto dilutivo y de arrastre sobre el transporte de oxígeno a través de la membrana. Se ha observado que, aunque el efecto de arrastre tenga menor importancia que el dilutivo, su efecto es importante ya que previene la formación de concentraciones de polarización. El estudio de electrolizadores que utilizan conductores protónicos sólidos de alta temperatura ha permitido estudiar el efecto del escalado en este proceso y evaluar la eficiencia en el almacenamiento de energía. El modelo de un reactor de membrana electroquímico basado en conductores protónicos integrado en un reformador de metano ha permitido comprobar que la demanda térmica del proceso se cubre por el efecto Joule y la electrocompresión del hidrógeno. Se ha comprobado como el coarsening observado en las partículas de níquel no limita la extracción de hidrógeno para la celda estudiada. Un último modelo fue construido para estudiar un reactor de membrana para el proceso de deshidrogenación de metano utilizando una celda co-iónica. El modelo fue validado utilizando datos experimentales. Se utilizó el modelo validado para realizar estudios para analizar posibles limitaciones del proceso. Finalmente, se ha comprobado que el desplazamiento del equilibrio de reacción mediante la extracción de hidrógeno se frena debido a limitaciones cinéticas. / [CA] Esta tesi presenta resultats sobre reactors de membrana a alta temperatura. Dos blocs diferenciades poden ser identificats: (i) treball experimental; (ii) treball de modelat. En el bloc experimental, elèctrodes basats en coure han siguts optimitzats per a tubular cells de conductor protòniques. La deposició de la capa basada en coure es va fer amb diferents tècniques. La tècnica de dip-coating ha sigut usada per a depositar una capa de cermet basada en coure. Aquesta tècnica es molt sensible a les condicions amb les que es desenvolupa la deposició perquè causa canvis de varis ordres de magnitud en la resistència de polarització del elèctrode. A més, la tècnica de sputtering ha sigut triada per a depositar coure. Per a depositar correctament la capa de coure, altes temperatures durant la deposició foren requerides. El elèctrode optimitzat presenta resistències de polarització inferiors a 0.1 ¿·cm2. En el treball de modelat, la metodologia de elements finits va ser utilitzada per a modelar diferents fenòmens concernits a reactors de membrana de elevada temperatura. La permeació de oxigen per membranes de conducció mixta ha sigut modelada per a avaluar la importància de la dilució i del arrossegament. Els resultats mostren que, encara que el efecte dilutiu es predominant, el efecte del arrossegament no pot ser depreciat. Un adequat arrossegament del oxigen permeat es necessari per evitar polaritzacions en la concentració del oxigen els quals limitarien la permeació. El efecte del arrossegament es major quan el gas portador es mes pesat. El model per estudiar un procés de electròlisis basat en conductors protòniques a elevada temperatura ha permès estudiar l'efecte de l'escalat de aquest procés i avaluar l'eficiència en l'emmagatzemament d'energia. Modelant un reformador de membrana protònica ha permès comprovar la microintegració tèrmica de tots el fenòmens que tenen lloc en aquest procés. Aquest procés compren les reaccions de reformat, extracció electroquímica de hidrogen i electrocompressió del hidrogen generat. La electrocompressió del hidrogen és un procés isoterma que allibera la energia demanda en forma de calor. El model ha permès comprovar que l'engrossiment de les partícules de níquel no limita l'extracció de hidrogen. Un últim model va ser construït per estudiar l'extracció de hidrogen en un reactor de membrana per al procés de dehidroaromatizatió de metà. El reactor de membrana utilitza materials co-iòniques per l'extracció de hidrogen de la càmera de reacció. Aquest model va ser validat amb resultats experimentals. El model va mostrar que no hi ha limitacions amb la difusió del hidrogen. A més, el desplaçament del equilibri mediant l'extracció de hidrogen està limitat per la baixa activitat cinètica del procés. / [EN] In this thesis several studies were developed about membranes reactor at high temperature. Two differentiated blocks could be identified: (i) experimental works; (ii) modelling works. In the experimental block, electrodes based on copper was developed for tubular protonic based cells. The deposition of the copper layer on the tubes was developed by different techniques. Dip-coating method was optimized to a copper-based cermet on the tube. Conditions of the dip-coating procedure has a critical impact in the final performance of the electrochemical cell whose supposes several orders of magnitude in the polarization resistance. It is a sensitive process with the defect of the tube as shows the copper spread over these defects. Additionally, sputtering technique was used to deposit copper layer on the tube. High temperature is required to achieve suitable attachments copper-tube. This high temperature deposited layer present polarization resistances lower than 0.1 ¿·cm2. In the modelling block, finite element methodology was used to build different models to study different phenomena concerning membrane reactors at high temperature. It was studied: (i) the oxygen permeation across a mixed ionic and electronic conducting membrane; (ii) water electrolysis based on high temperature protonic cells; (iii) hydrogen extraction from a steam methane reforming using a protonic cell; (iv) the intensification of the methane dehydromatization reactor using co-ionic membrane. Oxygen permeation model was built to evaluate the effect of the dilutive and the sweep contribution over the permeation process. The fitted model allowed the importance of the dilutive and sweep effect over the oxygen permeation. Although the sweep effect present lower influence in the oxygen transport across the membrane, its effect prevents concentration polarization limitations. Modelling the protonic cell based electrolysis allowed to study the effect of the scale up in this process and to evaluate the efficiency in the energy storing in form of hydrogen. Modelling protonic membrane reformer allowed checking the thermal microintegration of all the heats which take place in the setup. The electrocompression of hydrogen is an isothermal phenomenon which releases the demanded energy as heat. The model allowed to check the coarsening of the Ni particles does not limit the hydrogen extraction for the studied cell. A final model was built to study a catalytic membrane reactor for the methane dehydroaromatization using co-ionic conducting cells. The model was validated using experimental data. Additionally, different studies were performed to analyze possible limitation in the process. Results show that there are no hydrogen diffusion limitations in this process. Additionally, the shift of the equilibrium by extracting hydrogen has to be stopped because kinetic limitations. / Catalán Martínez, D. (2019). Development of electrocatalytic layers and thermo-fluid dynamic evaluation for high temperature membrane reactors [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/135278

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