Les complexes de polyélectrolytes (PECs) sont typiquement formés par interaction électrostatique entre deux polyélectrolytes de charge opposée. Alors que de nombreuses études ont été consacrées aux propriétés de ces complexes, l'objectif de la thèse est de mieux comprendre le rôle de l’intensité de l’interaction entre deux polyélectrolytes sur la morphologie des complexes ainsi que la cinétique et la thermodynamique de la complexation. Différents systèmes complexants, faibles et forts, donnant lieu à la formation de coacervats ou de précipités ont été choisis et étudiés sur une large gamme de rapport de charges (Z[+]/[-]) afin d'obtenir différents états physiques (soluble, colloïdal, phase dense). La morphologie des complexes a été déterminée par microscopie (optique, fluorescence, force atomique) et diffusion de rayonnement (lumière, neutrons). La cinétique et la thermodynamique de complexation ont été étudiées par utilisation respective d'un mélangeur à flux stoppé et de la calorimétrie de titration isotherme. Les résultats obtenus permettent de mettre en évidence un certain nombre de caractéristiques permettant de distinguer les systèmes complexants forts et faibles. En particulier, les complexes forts sont hors équilibre d'un point de vue thermodynamique et en conséquence ils présentent une forte dépendance aux conditions initiales de complexation. Un autre aspect important et qui pourrait être à l'origine de la distinction entre les complexes forts et faibles est l'énergie d'hydratation des polyélectrolytes qui a été déterminée pour de nombreux polyélectrolytes et corrélée aux propriétés des complexes. / Complexes of polyelectrolytes (PECs) are oppositely charged polymers assemblies held together by electrostatic interaction. As the non-covalent assembly of macromolecules/colloids in solution has been thoroughly investigated over the last decade with a particular emphasis put on the morphology of the final aggregates as a function of the building blocks-chemistry, the objective of this thesis is to come to a better understanding of the influence of interaction strength between polyelectrolytes on complexes morphologies, as well as kinetics and thermodynamics of the complexation. For this study, weakly and strongly interacting systems given rise to coacervate and precipitate phases has been elected. Those systems have been studied on a wide charge ratio scale (Z[+]/[-]) to span several physical states of the PECs (soluble and colloidal PECs, dense phases). Morphologies of assemblies are assessed by microscopy (optical, fluorescence, atomic force) and scattering techniques (neutron, light). Kinetics and thermodynamics of the complexation process are studied by use of a stopped-flow mixing device and an isothermal titration calorimeter. Results gave us keys to discriminate strongly interacting systems from weakly interacting ones. In particular, the ‘strong systems’ are showed to be non-equilibrium assemblies, ie. the formulation pathway or the way these different macromolecules are coming into contact is then a key step. Another important aspect that could explain the complexation process behavior is the hydration energy of the polyelectrolytes. Calorimetry measurements have been performed for numerous polyelectrolytes and then correlated to complexes properties.

To show how predaceous fish and dragonflies affect benthic community structure, we conducted enclosure experiments in the littoral zone of Bays Mountain Lake, Tennessee. A 'natural' benthic assemblage was subjected to all combinations of 2 densities of 3 predator treatments - small sunfish, 0 or 4/m2; large dragonfly larvae, 0 or 15/m2; and dragonfly eggs at 2 densities, 90 or 900/m2. Treatments were assigned randomly in each of 6 spatiotemporal blocks. Net effects of predation over 4 mo show that small sunfish had 'strong' effects (>50% reduction of densities) on triclads, large daphnid cladocerans, and snails, and 'moderate' effects (50% > reduction > 25%) on small dragonflies and ostracods; all these effects were statistically significant, except the one on ostracods. Large dragonflies had moderate non-significant effects on triclads and ostracods. There were no significant increases in prey density associated with fish predation; but chydorid cladocerans and midge larvae showed 'weak' non-significant increases that might be caused by 'indirect effects' of fish predation on invertebrate predators or grazers. There were only 2 significant interaction terms indicative of 'higher-order interactions': Fish X Dragonfly on the large daphnid Simocephalus, and Fish X Egg Density on snails, which were associated with relatively low probabilities. In both cases, the net effect of dragonflies was to reduce prey densities more when fish were present.

Le calcul de la réponse macroscopique des agrégats polycristallins à partir des propriétés de leurs constituants est un problème important en mécanique des matériaux. Lors de la déformation plastique, les grains du matériau sont réorientés. Une texture cristallographique, responsable de l'anisotropie, peut alors se développer. Donc, la modélisation de l'évolution de la texture est importante afin de prévoir les effets d'anisotropie lors des procédés industriels.La formulation de la plasticité des polycristaux métalliques a fait l'objet de nombreuses études et différentes approches d’homogénéisation ont été proposées. En 2008, Ahzi et M'Guil ont développé un modèle viscoplastique, baptisé le modèle-phi. Ce modèle prend en compte les effets d'interaction entre les grains sans passer par la théorie de l'inclusion d’Eshelby. Dans ce travail, le modèle-phi a été appliqué à différentes structures cristallographiques et sous différentes conditions de chargement. Le mécanisme de maclage a été pris en compte. Pour le laminage des métaux CFC, la transition de texture du type cuivre au type laiton a été étudiée. L’essai de cisaillement des métaux CFC a été également étudié. Nous montrons que le modèle est capable de prédire une transition de texture de cisaillement caractérisant une gamme de métaux CFC ayant une EDE élevée/moyenne à une EDE faible. Dans une étude dédiée aux métaux CC, nous avons comparé nos résultats à ceux prédits par un modèle auto-cohérent. Nous présentons également une comparaison avec des textures expérimentales de laminage à froid issues de la littérature. Le modèle a également été étendu aux métaux HC. Nous avons simulé le comportement de déformation d’un alliage de magnésium pour différentes niveaux d'interaction inter-granulaire. Nous montrons que le modèle prédit des résultats en bon accord avec les résultats expérimentaux. / The computation of the macroscopic response of polycrystalline aggregates from the properties of their single-crystal is a main problem in materials mechanics. During the mechanical deformation processing, all the grains in the polycrystalline material sample are reoriented. A crystallographic texture may thus be developed which is responsible for the material anisotropy. Therefore, the modeling of the texture evolution is important to predict the anisotropy effects present in industrial processes. The formulation of polycrystals plasticity has been the subject of many studies and different approaches have been proposed. Ahzi and M’Guil developed a viscoplastic phi-model. This model takes into account the grains interaction effects without involving the Eshelby inclusion problems.In this thesis, the phi-model was applied to different crystallographic structures and under different loading conditions. The mechanical twinning has been taken into account in the model. The FCC rolling texture transition from copper-type to brass-type texture is studied. The shear tests in FCC metals are also studied. The predicted results are compared with experimental shear textures for a range of metals having a high SFE to low SFE. For BCC metal, we compare our predicted results with those predicted by the VPSC model. We study the slip activities, texture evolutions and the evolution of yield loci. We also present a comparison with experimental textures from literatures for several BCC metals under cold rolling tests. The model has also been extended to HCP metals. We predict the deformation behavior of the magnesium alloy for different interaction strengths. We also compare our predicted results with experimental data from literatures. We show that the results predicted by the phi-model are in good agreement with the experimental ones.

The computation of the macroscopic response of polycrystalline aggregates from the properties of their single-crystal is a main problem in materials mechanics. During the mechanical deformation processing, all the grains in the polycrystalline material sample are reoriented. A crystallographic texture may thus be developed which is responsible for the material anisotropy. Therefore, the modeling of the texture evolution is important to predict the anisotropy effects present in industrial processes. The formulation of polycrystals plasticity has been the subject of many studies and different approaches have been proposed. Ahzi and M'Guil developed a viscoplastic phi-model. This model takes into account the grains interaction effects without involving the Eshelby inclusion problems.In this thesis, the phi-model was applied to different crystallographic structures and under different loading conditions. The mechanical twinning has been taken into account in the model. The FCC rolling texture transition from copper-type to brass-type texture is studied. The shear tests in FCC metals are also studied. The predicted results are compared with experimental shear textures for a range of metals having a high SFE to low SFE. For BCC metal, we compare our predicted results with those predicted by the VPSC model. We study the slip activities, texture evolutions and the evolution of yield loci. We also present a comparison with experimental textures from literatures for several BCC metals under cold rolling tests. The model has also been extended to HCP metals. We predict the deformation behavior of the magnesium alloy for different interaction strengths. We also compare our predicted results with experimental data from literatures. We show that the results predicted by the phi-model are in good agreement with the experimental ones.

No description available.

Most climate change predictions focus on the response of individual species to changing local conditions and ignore species interactions, largely due to the lack of a sound theoretical foundation for how interactions are expected to change with climate and how to incorporate them into climate change models. Much of the variability in species interaction strengths may be governed by fundamental constraints on physiological rates, possibly providing a framework for including species interactions into climate change models. Metabolic rates, ingestion rates and many other physiological rates are relatively predictable from body size and body temperature due to constraints imposed by the physical and chemical laws that govern fluid dynamics and the kinetics of biochemical reaction times. My dissertation assesses the usefulness of this framework by exploring the community-level consequences of physiological constraints. In Chapter 2, I incorporated temperature and body size scaling into the biological rate parameters of a series of realistically structured trophic network models. The relative magnitude of the temperature scaling parameters affecting consumer energetic costs (metabolic rates) and energetic gains (ingestion rates) determined how consumer energetic efficiency changed with temperature. I systematically changed consumer energetic efficiency and examined the sensitivity of network stability and species persistence to various temperatures. I found that a species' probability of extinction depended primarily on the effects of organismal physiology (body size and energetic efficiency with respect to temperature) and secondarily on the effects of local food web structure (trophic level and consumer generality). This suggests that physiology is highly influential on the structure and dynamics of ecological communities. If consumer energetic efficiency declined as temperature increased, that is, species did best at lower temperatures, then the simulated networks had greater stability at lower temperatures. The opposite scenario resulted in greater stability at higher temperatures. Thus, much of the community-level response depends on what species energetic efficiencies at the organismal-level really are, which formed the research question for Chapter 3: How does consumer energetic efficiency change with temperature? Existing evidence is scarce but suggestive of decreasing consumer energetic efficiency with increasing temperature. I tested this hypothesis on seven rocky intertidal invertebrate species by measuring the relative temperature scaling of their metabolic and ingestion rates as well as consumer interaction strength under lab conditions. Energetic efficiencies of these rocky intertidal invertebrates declined and species interaction strengths tended to increase with temperature. Thus, in the rocky intertidal, the mechanistic effect of temperature would be to lower community stability at higher temperatures. Chapter 4 tests if the mechanistic effects of temperature on ingestion rates and species interaction strengths seen in the lab are apparent under field conditions. Bruce Menge and I related bio-mimetic estimates of body temperatures to estimates of per capita mussel ingestion rates and species interaction strengths by the ochre sea star Pisaster ochraceus, a keystone predator of the rocky intertidal. We found a strong, positive effect of body temperature on both per capita ingestion rates and interaction strengths. However, the effects of season and the unique way in which P. ochraceus regulates body temperatures were also apparent, leaving room for adaptation and acclimation to partially compensate for the mechanistic constraint of body temperature. Community structure of the rocky intertidal is associated with environmental forcing due to upwelling, which delivers cold, nutrient rich water to the nearshore environment. As upwelling is driven by large-scale atmospheric pressure gradients, climate change has the potential to affect a wide range of significant ecological processes through changes in water temperature. In Chapter 5, my coauthors and I identified long-term trends in the phenology of upwelling events that are consistent with climate change predictions: upwelling events are becoming stronger and longer. As expected, longer upwelling events were related to lower average water temperatures in the rocky intertidal. Furthermore, recruitment rates of barnacles and mussels were associated with the phenology of upwelling events. Thus climate change is altering the mode and the tempo of environmental forcing in nearshore ecosystems, with ramifications for community structure and function. Ongoing, long-term changes in environmental forcing in rocky intertidal ecosystems provide an opportunity to understand how temperature shapes community structure and the ramifications of climate change. My dissertation research demonstrates that the effect of temperature on organismal performance is an important force structuring ecological communities and has potential as a tractable framework for predicting the community level effects of climate change. / Graduation date: 2013 / Access restricted to the OSU Community, at author's request, from Nov. 20, 2012 - Nov. 20, 2014

Tesis por compendio / [EN] Phononic crystals are artificial materials formed by a periodic arrangement of inclusions embedded into a host medium, where each of them can be solid or fluid. By controlling the geometry and the impedance contrast of its constituent materials, one can control the dispersive properties of waves, giving rise to a huge variety of interesting and fundamental phenomena in the context of wave propagation. When a propagating wave encounters a medium with different physical properties it can be transmitted and reflected in lossless media, but also absorbed if dissipation is taken into account. These fundamental phenomena have been classically explained in the context of homogeneous media, but it has been a subject of increasing interest in the context of periodic structures in recent years as well. This thesis is devoted to the study of different effects found in sonic and phononic crystals associated with transmission, reflection and absorption of waves, as well as the development of a technique for the characterization of its dispersive properties, described by the band structure. We start discussing the control of wave propagation in transmission in conservative systems. Specifically, our interest is to show how sonic crystals can modify the spatial dispersion of propagating waves leading to control the diffractive broadening of sound beams. Making use of the spatial dispersion curves extracted from the analysis of the band structure, we first predict zero and negative diffraction of waves at frequencies close to the band-edge, resulting in collimation and focusing of sound beams in and behind a 3D sonic crystal, and later demonstrate it through experimental measurements. The focusing efficiency of a 3D sonic crystal is limited due to the strong scattering inside the crystal, characteristic of the diffraction regime. To overcome this limitation we consider axisymmetric structures working in the long wavelength regime, as a gradient index lens. In this regime, the scattering is strongly reduced and, in an axisymmetric configuration, the symmetry matching with acoustic sources radiating sound beams increase its efficiency dramatically. Moreover, the homogenization theory can be used to model the structure as an effective medium with effective physical properties, allowing the study of the wave front profile in terms of refraction. We will show the model, design and characterization of an efficient focusing device based on these concepts. Consider now a periodic structure in which one of the parameters of the lattice, such as the lattice constant or the filling fraction, gradually changes along the propagation direction. Chirped crystals represent this concept and are used here to demonstrate a novel mechanism of sound wave enhancement based on a phenomenon known as "soft" reflection. The enhancement is related to a progressive slowing down of the wave as it propagates along the material, which is associated with the group velocity of the local dispersion relation at the planes of the crystal. A model based on the coupled mode theory is proposed to predict and interpret this effect. Two different phenomena are observed here when dealing with dissipation in periodic structures. On one hand, when considering the propagation of in-plane sound waves in a periodic array of absorbing layers, an anomalous decrease in the absorption, combined with a simultaneous increase of reflection and transmission at Bragg frequencies is observed, in contrast to the usual decrease of transmission, characteristic in conservative periodic systems at these frequencies. For a similar layered media, backed now by a rigid reflector, out-of-plane waves impinging the structure from a homogeneous medium will increase dramatically the interaction strength. In other words, the time delay of sound waves inside the periodic system will be considerably increased resulting in an enhanced absorption, for a broadband spectral range. / [ES] Los cristales fonónicos son materiales artificiales formados por una disposición periódica de inclusiones en un medio, pudiendo ambos ser de carácter sólido o fluido. Controlando la geometría y el contraste de impedancias entre los materiales constituyentes se pueden controlar las propiedades dispersivas de las ondas. Cuando una onda propagante se encuentra un medio con diferentes propiedades físicas puede ser transmitida y reflejada, en medios sin pérdidas, pero también absorbida, si la disipación es tenida en cuenta. La presente tesis está dedicada al estudio de diferentes efectos presentes en cristales sónicos y fonónicos relacionados con la transmisión, reflexión y absorción de ondas, así como el desarrollo de una técnica para la caracterización de sus propiedades dispersivas, descritas por la estructura de bandas. En primer lugar, se estudia el control de la propagación de ondas en transmisión en sistemas conservativos. Específicamente, nuestro interés se centra en mostrar cómo los cristales sónicos son capaces de modificar la dispersión espacial de las ondas propagantes, dando lugar al control del ensanchamiento de haces de sonido. Haciendo uso de las curvas de dispersión espacial extraídas del análisis de la estructura de bandas, se predice primero la difracción nula y negativa de ondas a frecuencias cercanas al borde de la banda, resultando en la colimación y focalización de haces acústicos en el interior y detrás de un cristal sónico 3D, y posteriormente se demuestra mediante medidas experimentales. La eficiencia de focalización de un cristal sónico 3D está limitada debido a las múltiples reflexiones existentes en el interior del cristal. Para superar esta limitación se consideran estructuras axisimétricas trabajando en el régimen de longitud de onda larga, como lentes de gradiente de índice. En este régimen, las reflexiones internas se reducen fuertemente y, en configuración axisimétrica, la adaptación de simetría con fuentes acústicas radiando haces de sonido incrementa la eficiencia drásticamente. Además, la teoría de homogenización puede ser empleada para modelar la estructura como un medio efectivo con propiedades físicas efectivas, permitiendo el estudio del frente de ondas en términos refractivos. Se mostrará el modelado, diseño y caracterización de un dispositivo de focalización eficiente basado en los conceptos anteriores. Considérese ahora una estructura periódica en la que uno de los parámetros de la red, sea el paso de red o el factor de llenado, cambia gradualmente a lo largo de la dirección de propagación. Los cristales chirp representan este concepto y son empleados aquí para demostrar un mecanismo novedoso de incremento de la intensidad de la onda sonora basado en un fenómeno conocido como reflexión "suave". Este incremento está relacionado con una ralentización progresiva de la onda conforme se propaga a través del material, asociado con la velocidad de grupo de la relación de dispersión local en los planos del cristal. Un modelo basado en la teoría de modos acoplados es propuesto para predecir e interpretar este efecto. Se observan dos fenómenos diferentes al considerar pérdidas en estructuras periódicas. Por un lado, si se considera la propagación de ondas sonoras en un array periódico de capas absorbentes, cuyo frente de ondas es paralelo a los planos del cristal, se produce una reducción anómala en la absorción combinada con un incremento simultáneo de la reflexión y transmisión a las frecuencias de Bragg, de forma contraria a la habitual reducción de la transmisión, característica de sistemas periódicos conservativos a estas frecuencias. En el caso de la misma estructura laminada en la que se cubre uno de sus lados mediante un reflector rígido, la incidencia de ondas sonoras desde un medio homogéneo, cuyo frente de ondas es perpendicular a los planos del cristal, produce un gran incremento de la fuerza de / [CA] Els cristalls fonònics són materials artificials formats per una disposició d'inclusions en un medi, ambdós poden ser sòlids o fluids. Controlant la geometría i el contrast d'impedàncies dels seus materials constituents, és poden controlar les propietats dispersives de les ondes, permetent una gran varietatde fenòmens fonamentals interessants en el context de la propagació d'ones. Quan una ona propagant troba un medi amb pèrdues amb propietats físiques diferents es pot transmetre i reflectir, però també absorbida si la dissipació es té en compte. Aquests fenòmens fonamentals s'han explicat clàssicament en el context de medis homogenis, però també ha sigut un tema de creixent interés en el context d'estructures periòdiques en els últims anys. Aquesta tesi doctoral tracta de l'estudi de diferents efectes en cristalls fonònics i sònics lligats a la transmissió, reflexió i absorció d'ones, així com del desenvolupament d'una tècnica de caracterització de les propietats dispersives, descrites mitjançant la estructura de bandes. En primer lloc, s'estudia el control de la propagació ondulatori en transmissió en sistemes conservatius. Més específicament, el nostre interés és mostrar com els cristalls sonors poden modificar la dispersió espacial d'ones propagants donant lloc al control de l'amplària per difracció dels feixos sonors. Mitjançant les corbes dispersió espacial obtingudes de l'anàlisi de l'estructura de bandes, es prediu, en primer lloc, la difracció d'ones zero i negativa a freqüències próximes al final de banda. El resultat és la collimació i focalització de feixos sonors dins i darrere de cristalls de so. Després es mostra amb mesures experimentals. L'eficiència de focalització d'un cristall de so 3D està limitada per la gran dispersió d'ones dins del cristall, que és característic del règim difractiu. Per a superar aquesta limitació, estructures axisimètriques que treballen en el règim de llargues longituds d'ona, i es comporten com a lents de gradient d'índex. En aquest règim, la dispersió es redueix enormement i, en una configuració axisimètrica, a causa de l'acoblament de la simetría amb les fonts acústiques que radien feixos sonors, l'eficiència de radiació s'incrementa significativament. D'altra banda, la teoria d'homogeneïtzació es pot utilitzar per a modelar, dissenyar i caracteritzar un dispositiu eficient de focalització basat en aquests conceptes. Considerem ara una estructura periòdica en la qual un dels seus paràmetres de xarxa, com ara la constant de xarxa o el factor d'ompliment canvia gradualment al llarg de la direcció de propagació. Els cristalls chirped representen aquest concepte i s'utilitzen ací per a demostrar un mecanisme nou d'intensificació d'ones sonores basat en el fenòmen conegut com a reflexió "suau". La intensificació està relacionada amb la alentiment progressiva de l'ona conforme propaga al llarg del material, que està associada amb la velocitat de grup de la relació de dispersió local en els diferents plànols del cristall. Es proposa un model basat en la teoria de modes acoblats per a predir i interpretar este efecte. Dos fenòmens diferents cal destacar quan es tracta d'estructures periòdiques amb dissipació. Per un costat, al considerar la propagació d'ones sonores en el plànol en un array periòdic de capes absorbents, s'observa una disminució anòmala de l'absorció i es combina amb un augment simultani de reflexió i transmissió en les freqüències de Bragg que contrasta amb la usual disminució de transmissió, característica dels sistemes conservatius a eixes freqüències. Per a un medi similar de capes, amb un reflector rígid darrere, les ones fora del pla incidint l'estructura des de un medi homogeni, augmentaran considerablement la interacció. En altres paraules, el retràs temporal de les ones sonores dins del sistema periòdic augmentarà significativament produint un augmen / Cebrecos Ruiz, A. (2015). Transmission, reflection and absorption in Sonic and Phononic Crystals [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/56463 / Premios Extraordinarios de tesis doctorales / Compendio