Carbon dioxide electroreduction (CO2R) is a promising and sustainable route to generate valuable feedstocks through the electrochemical conversion from CO2 with electricity generated by renewable energy resources, to reduce greenhouse gas emissions, thereby protecting the global environment. One of the critical challenges for developing practical CO2R developments is understanding the structures and chemistry of CO2R electrocatalysts, and then generating fundamental insights to guide the design and optimization of high-performance electrocatalysts. During my Ph.D. studies, synchrotron-based X-ray spectro-microscopy techniques, scanning transmission X-ray microscopy (STXM) and X-ray spectro-ptychography, were used to study nickel-nitrogen-carbon (Ni-N-C) and electrodeposited Cu-based CO2R electrocatalysts. STXM and ptychography were upgraded to in situ characterizations to provide spectroscopic characterization and quantitative, chemically selective imaging of these catalytic materials under CO2R conditions. To achieve in situ STXM and spectro-ptychography, a micro-fluidic based, liquid-flow electrochemical in situ device was developed, fabricated, and implemented. The in situ device is optimized from previous versions developed by Vinod Prabu, past graduate student of Hitchcock group, and the initial concept was provided by Pablo Ingino and Dr. Martin Obst, collaborators at the University of Bayreuth. In situ STXM and spectro-ptychography provided a detailed chemical and morphological evaluation of catalyst materials at different applied potentials during electrochemical processes. The in situ STXM studies of Cu-based catalysts showed that electrodeposited Cu2O particles are converted to metallic Cu with different reaction rates at applied potentials less negative than that for initiation of CO2R. The in situ STXM results show a degree of heterogeneity in the electrochemical response of discrete nanoparticles and metallic Cu as the active catalyst for CO2 reduction which is structurally relatively stable at CO2R-relevant potentials within the spatial resolution of STXM. In situ spectra-ptychography was used to follow morphological changes of a single Cu-based catalytic particle in the electrochemical regime of CO2R. Our results show that the Cu particle lost the initial cubic structure and formed irregular dendritic-like structures during the CO2R process. To the best of my knowledge, this is the first time in situ STXM has been applied to CO2R electrocatalysts under flow liquid and electrochemical conditions and the first report of in situ spectro-ptychography studies. In summary, my research has successfully achieved the in situ STXM and spectro-ptychography experiments and contributed to an improved understanding of Cu nanoparticle CO2R electrocatalysts. / Dissertation / Doctor of Philosophy (PhD)

Baseando-se na possibilidade de inserção de um novo material de origem têxtil natural animal, bem como, a reciclagem de aproximadamente 1,175 milhões de toneladas descartadas anualmente da matéria-prima estudada (UBABEF, 2011), esta pesquisa teve como objetivo geral efetuar a caracterização física e microscópica de fibra de pena de frango para finalidade têxtil seja para o desenvolvimento de fios têxteis, não tecidos e reforço em compósitos ou outras aplicações. Deste modo, foram objetivos: i) realizar levantamento bibliográfico sobre estrutura e composição de penas e fibras de penas, reciclagem, aplicações existentes, técnicas e processos de caracterização da fibra; ii) coleta do material fibroso proveniente de um matadouro doméstico de frangos; iii) preparação do material, lavagem e secagem das penas; iv) testes mecânicos de caracterização como: alongamento, elasticidade e resistência realizados por meio do dinamômetro Instrom, determinação do teor de regain, umidade e densidade da fibra, bem como a taxa de encolhimento da fibra; v) testes microscópicos de caracterização como: microscopias longitudinais e transversais; vi) propostas e direcionamento do emprego das fibras caracterizadas para finalidade de produção têxtil. As principais conclusões foram: i) bibliografia inédita em português sobre penas de frango para a área têxtil; ii) estudo inédito no Brasil e na língua portuguesa de propriedades físicas e microscópicas de fibras de pena de frango; iii) com base em suas propriedades estruturais, perceberam-se características como brilho, conforto, maciez, toque, permeabilidade à líquido, leveza, entre outras propriedades, aumentando assim seu potencial de empregabilidade têxtil; iv) potencial de fiação e fabricação de têxteis para diversas aplicações. Publicações e palestras foram realizadas com os resultados desta dissertação. / Based on the possibility of developing a new textile material of natural animal origin, as well as the recycling of the studied raw material, of which approximately 1.175 million tons are annually discarded as waste in Brazil (UBABEF, 2011), this study aimed to characterize the general physical and microscopical fibers of chicken feathers for textile purpose for the development of textile yarn, non-woven and composite reinforcement. Its objectives were: i) to analyze the academic literature about the structure and composition of feathers and feather fibers, as well as its recycling, existing applications, processes and techniques of fiber characterization, ii) the collection of fibrous material from a chicken slaughterhouse, iii) the preparation of material, washing and drying the feathers, iv) to develop mechanical characterization tests such as elongation, elasticity and resistance made by Instrom dynamometer, determining the content, moisture regain and fiber density, v) to perform the microscopic characterization tests such as microscopy longitudinal and transverse, and vi ) to draft proposals on the employment of the analyzed and characterized fibers for purposes of producing textiles (yarns, reinforcement for composites, nonwoven blankets, etc.). The main findings were: i) unpublished literature in Portuguese about chicken feathers for the textile area, ii) unpublished study in Brazil and in portuguese language of physical and microscopic properties of chicken feathers\' fibers for the development of textile products of natural origin from such chicken feathers, iii) the identification of the potential for the production of blended yarn with cotton / wool, blankets and non-woven and reinforcement for composites, based on their physical, mechanical and microscopic properties, and, iv) the identification of the potential for yarn production (via spinning) and textile manufacturing for various applications. Publications and lectures were held with the results of this dissertation.

Cette étude concerne l’influence de la formulation sur les propriétés en fatigue des élastomères. Pour cela, douze matériaux ont été préalablement choisis de façon à ce que leur formulation soit simplifiée mais représentative de celles de matériaux industriels. La première partie de l’étude vise la description des mécanismes et des scénarios d’endommagement par fatigue, pour différents matériaux, niveaux de sollicitation et pourcentages de durée de vie. Une vaste campagne d’essais de fatigue interrompus a été menée permettant une analyse statistique de la population de défauts. Ces données ont permis d’une part de proposer des scénarios de ruine pour les différents matériaux étudiés, et d’autre part d’identifier deux types de mécanismes d’amorçage autour d’inclusions de différentes natures. La deuxième partie de l’étude vise à comprendre les mécanismes d’amorçage de fissure de fatigue. Un protocole expérimental permettant d’obtenir les champs d’énergie dissipée directement à partir des champs de température mesurés a été mis en place. Ce protocole a d’abord été développé à une échelle macroscopique et validé grâce à des simulations par éléments finis. Il a ensuite été appliqué avec succès à l’échelle des inclusions pour des cas 2D. Enfin, la troisième partie de cette étude propose un critère énergétique basé sur un protocole d’auto-échauffement permettant une détermination rapide des propriétés en fatigue. L’approche proposée utilise un critère à deux paramètres et permet de prédire la courbe de Wöhler déterministe avec une seule éprouvette, en une demi-journée d’essai et uniquement à partir de mesures thermiques. Ce critère a été validé sur une large gamme d’élastomères, et s’avère capable de rendre compte de l’influence de la gomme, du taux et du type de charges. / This study deals with the influence of the formulation on the fatigue properties of elastomeric materials. Twelve materials have been chosen so that their formulations are simplified but representative of these used in the industry. The first part of the study aims to describe the fatigue damage mechanisms and scenarios, for different materials, strain levels and fatigue life durations. A large experimental campaign of interrupted fatigue tests has been performed enabling a statistical analysis of the defects population. On one hand, these data led to propose damage scenarios for the studied materials, and on the other hand, to identify two classes of initiation mechanisms around different nature of inclusions. The second part of this study aims to better understand the fatigue crack initiation mechanisms. An experimental protocol enabling to obtain directly the dissipated energy fields from the measurement of the temperature fields has been set up. This protocol has been first developed at the macroscopic scale and validated thanks to numerical simulations. Then, it has been applied successfully at the scale of inclusions for 2D cases. Finally, the third part of this study suggests an energetic criterion based on a heat build-up protocol leading a fast determination of the fatigue properties. This approach uses a criterion with two parameters and is able to predict the deterministic Wöhler curve with one sample, in half a day and thanks to thermal measurements only. This criterion has been validated on a wide range of elastomeric materials and is able to reflect the influence of the gum, the type and the amount of carbon black.

Baseando-se na possibilidade de inserção de um novo material de origem têxtil natural animal, bem como, a reciclagem de aproximadamente 1,175 milhões de toneladas descartadas anualmente da matéria-prima estudada (UBABEF, 2011), esta pesquisa teve como objetivo geral efetuar a caracterização física e microscópica de fibra de pena de frango para finalidade têxtil seja para o desenvolvimento de fios têxteis, não tecidos e reforço em compósitos ou outras aplicações. Deste modo, foram objetivos: i) realizar levantamento bibliográfico sobre estrutura e composição de penas e fibras de penas, reciclagem, aplicações existentes, técnicas e processos de caracterização da fibra; ii) coleta do material fibroso proveniente de um matadouro doméstico de frangos; iii) preparação do material, lavagem e secagem das penas; iv) testes mecânicos de caracterização como: alongamento, elasticidade e resistência realizados por meio do dinamômetro Instrom, determinação do teor de regain, umidade e densidade da fibra, bem como a taxa de encolhimento da fibra; v) testes microscópicos de caracterização como: microscopias longitudinais e transversais; vi) propostas e direcionamento do emprego das fibras caracterizadas para finalidade de produção têxtil. As principais conclusões foram: i) bibliografia inédita em português sobre penas de frango para a área têxtil; ii) estudo inédito no Brasil e na língua portuguesa de propriedades físicas e microscópicas de fibras de pena de frango; iii) com base em suas propriedades estruturais, perceberam-se características como brilho, conforto, maciez, toque, permeabilidade à líquido, leveza, entre outras propriedades, aumentando assim seu potencial de empregabilidade têxtil; iv) potencial de fiação e fabricação de têxteis para diversas aplicações. Publicações e palestras foram realizadas com os resultados desta dissertação. / Based on the possibility of developing a new textile material of natural animal origin, as well as the recycling of the studied raw material, of which approximately 1.175 million tons are annually discarded as waste in Brazil (UBABEF, 2011), this study aimed to characterize the general physical and microscopical fibers of chicken feathers for textile purpose for the development of textile yarn, non-woven and composite reinforcement. Its objectives were: i) to analyze the academic literature about the structure and composition of feathers and feather fibers, as well as its recycling, existing applications, processes and techniques of fiber characterization, ii) the collection of fibrous material from a chicken slaughterhouse, iii) the preparation of material, washing and drying the feathers, iv) to develop mechanical characterization tests such as elongation, elasticity and resistance made by Instrom dynamometer, determining the content, moisture regain and fiber density, v) to perform the microscopic characterization tests such as microscopy longitudinal and transverse, and vi ) to draft proposals on the employment of the analyzed and characterized fibers for purposes of producing textiles (yarns, reinforcement for composites, nonwoven blankets, etc.). The main findings were: i) unpublished literature in Portuguese about chicken feathers for the textile area, ii) unpublished study in Brazil and in portuguese language of physical and microscopic properties of chicken feathers\' fibers for the development of textile products of natural origin from such chicken feathers, iii) the identification of the potential for the production of blended yarn with cotton / wool, blankets and non-woven and reinforcement for composites, based on their physical, mechanical and microscopic properties, and, iv) the identification of the potential for yarn production (via spinning) and textile manufacturing for various applications. Publications and lectures were held with the results of this dissertation.

L’habitat sain est le thème central des réflexions contemporaines du domaine du bâtiment élargies à l’environnement. Il comporte des préoccupations notables en matière de santé, de consommation énergétique (la ventilation, le chauffage, la climatisation et l’eau chaude), d’impacts environnementaux et de durabilité des matériaux de construction. Le choix préliminaire des matériaux utilisés pour la construction joue un rôle important dans la réussite d’un projet HQE (Haute Qualité Environnementale). Dans ce contexte, la problématique de prévision des champs de température et d’humidité demeure essentielle à l’intérieur des matériaux poreux de construction, où les matériaux biosourcés font l'objet d'un fort intérêt vu leurs qualités environnementales. Les matériaux biosourcés, étant hygroscopiques, ont tendance à absorber ou à restituer l’humidité, ce qui génère respectivement un gonflement ou un retrait. A l’échelle microscopique, l’humidité prend place soit par l’absorption de l’eau liée par les fibres, soit par l’existence d’eau libre dans les pores. Cette complexité des phénomènes microscopiques dans les matériaux biosourcés mène à une forte interaction entre l’aspect mécanique et les aspects de transferts de masse et de chaleur. L’existence de ce couplage est susceptible de modifier sensiblement les performances thermiques du bâtiment, et même sa durabilité. L’objectif visé par ce travail de thèse est l’étude et l’analyse microscopique du comportement hygrique des matériaux poreux de construction. L’aspect mécanique couplé à l’aspect hygrique est abordé en prenant en considération les déformations locales de gonflement - retrait, et leur impact sur l’hystérésis de teneur en eau. La maîtrise de ce couplage est primordiale tant sur le plan de la prédiction de la qualité des ambiances habitables que sur l’évaluation de la durabilité de ces structures. Le projet de thèse consiste à travailler à la fois sur les aspects modélisation, caractérisation et mesure des transferts hygriques. La quantification de ces phénomènes est réalisée à travers des campagnes de mesures expérimentales basées sur des techniques d’imagerie 3D (micro-tomographie aux rayons X). Le recours à la diffraction aux rayons X (DRX), à la corrélation d’images volumique, ainsi qu’à la résonance magnétique nucléaire (RMN) permet d’avoir une meilleure compréhension des échanges entre la matrice solide et l’eau liée et/ou libre. Tous ces travaux ont mené à une meilleure caractérisation de la morphologie du bois d’épicéa à l’échelle microscopique, ainsi qu’à une meilleure estimation des diverses variations dimensionnelles (gonflement) à l’échelle des parois cellulaires et de leurs constituants chimiques. Les résultats numériques obtenus sur la structure réelle 3D du matériau ont été couplés aux mesures expérimentales à travers la corrélation d’images volumiques (micro-tomographie aux rayons X) afin d’identifier les propriétés intrinsèques des phénomènes et du matériau. Ces travaux de thèse constitueront une base scientifique permettant une meilleure modélisation du couplage mécanique avec les transferts de chaleur et de masse dans les matériaux biosourcés. / Healthy living is a main contemporary concern of the construction field, extended to the environment. It has significant concerns about health, energy consumption, environmental impact and sustainability of building materials. The preliminary selection of materials used for construction plays an important role in the success of high environmental quality projects. In this context, it remains essential to predict the temperature and humidity fields inside porous building materials, where bio-based materials are subject to a strong interest due to their environmental qualities.As bio-based materials are hygroscopic, they tend to absorb or restore moisture, which respectively generates swelling or shrinkage. At the microscopic scale, moisture takes place either by absorption of bound water by the fibers, or by the existence of free water in the pores. The complexity of microscopic phenomena in bio-based materials will lead to strong interactions between the mechanical aspect on one side and heat and mass transfers’ aspects on the other side. The existence of this coupling may significantly alter the building's thermal performance, as well as its durability.The objective of this thesis work is to study the microscopic hygric behavior of porous building materials. The mechanical aspect coupled to the hygric one is studied, taking into consideration the local swelling and shrinkage strains, and their impact on the hysteresis phenomenon. Understanding this coupling is very important in order to improve the quality of habitat and evaluate the durability of these structures.The PhD project consists on working on all aspects, modeling, characterization and measurement of hygric transfers. Quantification of these phenomena is achieved through experimental campaigns based on 3D imaging techniques (X-ray micro-tomography). The use of X-ray diffraction (XRD), digital volume correlation, as well as nuclear magnetic resonance (NMR) allows a better understanding of the interactions between the solid matrix and bound and/or free water. The corresponding results have led to a microscopic morphological characterization of spruce wood, as well as to a better estimation of the various dimensional variations of the cell walls, and their chemical components.The numerical results achieved on the real 3D structure of the material have been coupled to the experimental ones, using digital volume correlation technique (X-ray tomography), in order to identify the intrinsic properties of the material.These thesis works provide a scientific basis allowing the improvement of modeling of the mechanical coupling with heat and mass transfers in bio-based materials.

En la exploración de nuevos métodos para el mejoramiento de la eficiencia y rendimiento del motor diésel, es claro que un gran esfuerzo debe estar enfocado en el proceso de inyección de combustible. La eficiencia de la combustión y las emisiones, se ven muy afectadas por el proceso de atomización, y se ha demostrado que incrementos en presiones de inyección conllevan un gran potencial para mejorar el ahorro de combustible, producir mejores mezclas de aire y combustible, y por tanto menor generación de emisiones contaminantes. Últimamente, las presiones de inyección han aumentado de alrededor de 50 MPa en los años 70 hasta 250 MPa en los días actuales. Presiones de inyección muy altas (250-300 MPa) o incluso ultra altas (> 300 MPa) vienen siendo materia de investigación con el fin de ser implementadas de manera comercial en un futuro próximo. La estructura y desarrollo del spray diésel pueden ser caracterizados desde un punto de vista microscópico por medio de la medición del tamaño de gotas del spray y sus velocidades. En condiciones no-evaporativas, técnicas como el PDPA (Phase Doppler Particle Analyzer) vienen siendo utilizadas para la obtención de perfiles de diámetros y velocidades de gota con una alta resolución temporal. Desde el punto de vista macroscópico, existen parámetros específicos que permiten caracterizar a un chorro diésel, estos son: la penetración de vapor y líquida junto con el ángulo de apertura del chorro. La penetración líquida es un indicador claro de la capacidad de evaporación del combustible utilizado, mientras que la penetración de vapor, por su parte, es indicativo del proceso de mezcla y la probabilidad de colisión con las paredes de la cámara de combustión; factores claves a la hora de la generación de emisiones contaminantes. En esta tesis se estudia la influencia de presiones bajas, medias y muy altas presiones inyección, sobre un amplio espectro de condiciones y diagnósticos experimentales, y desde el punto de vista macroscópico y microscópico. Se realizaron experimentos para tres diferentes inyectores, 2 solenoides y un piezo eléctrico, este último con la capacidad de alcanzar presiones de inyección cercanas a 270 MPa. Las medidas incluyen una caracterización hidráulica, compuesta por tasa de inyección; una visualización de alta velocidad del chorro líquido isotermo; una visualización de alta velocidad del chorro inerte evaporativo, con captura simultánea de las fases líquida y vapor; y finalmente, una caracterización microscópica por medio de la obtención de distribución de tamaño de gotas y sus velocidades. Con respecto a los ensayos microscópicos, se desarrolló una metodología para el aislamiento y alineación de sprays con un error de medición muy bajo de 0,22°. Se llevaron a cabo mediciones de velocidad de gotas, cuyos resultados mostraron buen ajuste con perfiles teóricos de velocidad. De igual manera, una correlación para el tamaño de gota SMD se obtuvo mostrando un alto nivel de ajuste y siendo representativa para todo el rango de presiones de inyección estudiados. En el caso de la caracterización macroscópica del chorro isotermo, se han detectado variaciones macroscópicas en el desarrollo del chorro con propiedades de gas, inclusive en condiciones de motor comunes. Para estimar estos efectos y otros que las presiones de inyección muy altas tendrían sobre la estructura del chorro, se incentivó la aparición de ondas de choque controlando la velocidad del sonido del ambiente. Se usaron tres gases ambientales (SF6 N2 y CO2) con diferentes velocidades de sonido, promoviendo de esta manera chorros supersónicos en determinados casos. Al comparar ensayos con mismas densidades y diferentes gases ambientales, se encontró que todas las tendencias cercanas al estado transónico (0.8 <M <1.2) tenían una mayor penetración y menor ángulo de chorro. / En l'exploració de nous mètodes per al millorament de l'eficiència i rendiment del motor dièsel, és clar que un gran esforç s'ha enfocar en el procés d'injecció de combustible. L'eficiència de la combustió i les emissions, es veuen molt afectades pel procés d'atomització, i s'ha demostrat que increments en pressions d'injecció comporten un gran potencial per a millorar l'estalvi de combustible, produir millors mescles d'aire i combustible, i per tant menor generació d'emissions contaminants. Últimament, les pressions d'injecció han augmentat d'al voltant de 50 MPa en els anys 70 fins a 250 MPa en els dies actuals. Pressions d'injecció molt altes (250-300 MPa) o inclús ultra altes (> 300 MPa) vénen sent matèria d'investigació a fi de ser implementades de manera comercial en un futur pròxim. L'estructura i desenrotllament de l'esprai dièsel poden ser caracteritzats des d'un punt de vista microscòpic per mitjà del mesurament de la grandària de gotes de l'esprai i les seues velocitats. En condicions no-evaporatives, tècniques com el PDPA (Phase doppler particle analyzer) vénen sent utilitzades per a l'obtenció de perfils de diàmetres i velocitats de gota amb una alta resolució temporal. Des del punt de vista macroscòpic, hi ha paràmetres específics que permeten caracteritzar a un doll dièsel, estos són: la penetració de vapor i la penetració líquida junt amb l'angle d'obertura del doll. La penetració líquida és un indicador clar de la capacitat d'evaporació del combustible utilitzat, mentres que la penetració de vapor, per la seua banda, és indicatiu del procés de mescla i la probabilitat de col·lisió amb les parets de la cambra de combustió; factors claus a l'hora de la generació d'emissions contaminants. En esta tesi s'estudia la influència de pressions d' injecció baixes, mitges i molt altes, sobre un ampli espectre de condicions i diagnòstics experimentals, i des del punt de vista macroscòpic i microscòpic. Es van realitzar experiments per a tres injectors diferents, 2 solenoides i un piezo elèctric, este últim amb la capacitat d'aconseguir pressions d'injecció pròximes a 270 MPa. Les medides inclouen una caracterització hidràulica, composta per taxa d'injecció; una visualització d'alta velocitat del doll líquid isoterm; una visualització d'alta velocitat del doll inert evaporativo, amb captura simultània de les fases líquida i vapor; i finalment, una caracterització microscòpica per mitjà de l'obtenció de distribució de grandària de gotes i les seues velocitats. Respecte als assajos microscòpics, es va desenrotllar una metodologia per a l'aïllament i alineació d'esprais amb un error de mesurament molt davall de 0,22°. Es van dur a terme mesuraments de velocitat de gotes, els resultats van mostrar bon ajust amb perfils teòrics de velocitat. De la mateixa manera, una correlació per a la grandària de gota SMD es va obtindre mostrant un alt nivell d'ajust i sent representativa per a tot el rang de pressions d'injecció estudiats. En el cas de la caracterització macroscòpica del doll isoterm, s'han detectat variacions macroscòpiques en el desenrotllament del doll amb propietats de gas, inclusivament en condicions de motor comú. Per a estimar estos efectes i altres que altes pressions d'injecció tindrien sobre l'estructura del doll, es va incentivar l'aparició d'ones de xoc controlant la velocitat del so de l'ambient. Es van usar tres gasos ambientals (SF6, N2 i CO2) amb diferents velocitats de so, promovent d'esta manera dolls supersònics en determinats casos. Al comparar assajos amb mateixes densitats i diferents gasos ambientals, es va trobar que totes les tendències pròximes a l'estat transónic (0.8 < M < 1.2) tenien una major penetració i menor angle de doll. Respecte al doll evaporatiu, per a pressions d'injecció molt altes com 270MPa, els efectes dels paràmetres ambientals i d'injecció van romandre iguals respecte a totes les carac / In the exploration of new methods for improving the efficiency and performance of the diesel engine, it is clear that a great effort should be focused on the fuel injection process. The efficiency of combustion and emissions are greatly affected by the atomization process, and it is considered that injection pressures increments have a great potential to improve fuel economy, produce better air and fuel mixtures, and thus low generation of polluting emissions. Lately, injection pressures have increased from around 50 MPa in the 70's to 250 MPa in the current days, even very high injection pressures (250-300 MPa) or ultra high pressures (> 300 MPa) have been the subject of the scientific community in order to be implemented in future injection systems. The structure and development of the diesel spray can be characterized from a microscopic point of view by means of estimation of droplets size and velocities. At non-evaporative conditions, techniques such as PDPA (Phase Doppler Particle Analyzer) are being used to obtain diameters and velocity profiles a with high temporal resolution. From the macroscopic point of view, there are specific parameters that allow characterizing the diesel spray, these are: the liquid and vapor penetration along with the spray angle. The liquid penetration is a clear indicator of the evaporation capacity of the fuel used, whilst the vapor penetration, on the other hand, is an indicative of the mixing process and the probability of collision with the combustion chamber walls; key factors when generating polluting emissions. In this thesis the influence of low and very high injections pressures over the macro and micro characteristics of the diesel spray is studied, over a wide spectrum of conditions and experimental diagnoses. Experiments were carried out for three different injectors, two solenoids and one piezoelectric, the latter with the capacity to reach injection pressures close to 270MPa. The measurements include a hydraulic characterization; a high speed visualization of the liquid spray at isothermal conditions; a high-speed visualization of the evaporative spray, with simultaneous capture of the liquid and vapor phases; and finally, a microscopic characterization. Regarding the microscopic tests, a methodology was developed for the spray isolation and alignment with a very low measurement error of 0.22° Droplets velocity measurements were carried out, the results showed good adjustment with theoretical velocity profiles. Similarly, a correlation for SMD droplet size was obtained showing a high level of adjustment and being representative for the entire range of injection pressures studied. In the case of the macroscopic characterization of the isothermal spray, variations have been detected in the development of the jet with gas properties, even at common engine injection conditions. To estimate these effects and others that very high injection pressures would have on the spray structure, the apparition of shock waves was enhanced by controlling the speed of sound of the environment using three ambient gases with different speed of sound (SF6, N2 and CO2). When comparing tests with same densities and different ambient gases, it was found that all the tendencies near the transonic state (0.8 <M <1.2) had a higher penetration and lower spray angle. With respect to the evaporative jet, for very high injection pressures like 270MPa, the effects of the environmental and injection parameters remained the same with respect to all the macroscopic characteristics. / Giraldo Valderrama, JS. (2018). Macroscopic and microscopic characterization of non-reacting diesel sprays at low and very high injection pressures [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/113643

Concrete is the most widely used construction material worldwide, yet, it presents major sustainability drawbacks due to the CO2 released during the manufacturing of its main constituent, cement. Several approaches are used to improve concrete’s eco-efficiency and reduce the binder intensity index, a metric used to measure the eco-efficiency of concrete, to a value below that of conventional concrete mixtures (i.e., 10 kg/m3.MPa-1 for 25-40 MPa mixtures). Particle Packing Models (PPM) is consequently an approach that can be used to enhance system packing density, reducing cement content while increasing hardened state properties and durability (i.e., reducing porosity). However, packed mixtures normally present issues in the fresh state while their hardened state performance is not fully comprehended. Therefore, this Ph.D. project proposes a new mix-design method called PPM-MP approach to develop eco-efficient mixtures. First, a detailed laboratory investigation was conducted on mixtures developed using the proposed approach in order to understand their fresh and hardened state performance. Concrete samples containing distinct ranges of cement content (320, 250, 200, 150 kg/m3) and slump (180, 90, and 20 +/- 20 mm) were fabricated and a wide range of fresh state tests (pH, temperature, fresh density, air content, slump and rheology over time) and hardened state tests (apparent porosity, surface electrical resistivity, compressive strength, and modulus of elasticity) were performed over time. Then, its performance against the alkali-silica reaction (ASR) induced expansion and deterioration, which is one of the leading and most damaging distress mechanisms issues in durability, was evaluated. In this section of the project, four sustainable concrete mixtures developed with varying cement content (e.g., 325, 250, 200, and 150 kg/m3) were developed and compared to a control mixture containing 420 kg/m3 of cement content. The mixtures were tested over a year under Concrete prism test (CPT) setup, which is the current method used to evaluate concrete ASR and using three different non-boosted test setups (i.e., Wrapped - W, Soaked - S, and Encapsulated - E). Moreover, two distinct types of highly reactive aggregates (e.g., Springhill Greywacke coarse aggregate and Texas Polymictic sand) were selected. Microscopic analysis was used to better understand the impact of ASR on sustainable mixtures, as well as the differences in ASR-damage and crack propagation under different test protocols. The results show the feasibility of producing an eco-efficient mixture in a more efficient manner which may contribute to the Net Zero Concrete targets. The proposed PPM-MP approach improves the sustainability of concrete mixtures and can be used for specific projects requiring 28-day compressive strength ranging from 18 to 45 MPa and slumps (180, 90, and 20 +/- 20 mm).