Dans un contexte de valorisation de molécules issues de la biomasse, de nouvelles architectures moléculaires et polyols ont été développé à partir du sorbitol et divers synthons biosourcés en se basant autant que possible sur les principes de la chimie verte. A partir de réactions d’estérifications contrôlées plusieurs polyols polyesters ont été synthétisés, en l’absence de solvant. Grace à l’utilisation de diols de différentes tailles (C2 à C12) comme monomères, la viscosité et la teneur en fonctions hydroxyles des polyols finaux ont pu être adaptée jusqu’à obtention de propriétés satisfaisantes à l’élaboration de mousses polyuréthanes. Ainsi, des mousses polyuréthanes semi-flexible et des mousses polyisocyanurate rigides ont pu être formulés avec des profils cinétiques de moussage rapide (inférieur à 3 min). Les mousses polyisocyanurates rigides présentent d’excellente propriétés mécaniques et thermiques pouvant pleinement satisfaire à la l’isolation thermique de bâtiment. D’autre part, une voie de transestérification entre le sorbitol et diméthyle carbonate a été étudié afin d’élaborer une nouvelle molécule plateforme bi-fonctionnelle : un bis-cyclocarbonate. A partir de cette molécule plateforme des réactions de polymérisation par ouverture de cycles et d’aminolyses ont été mise en place pour la synthèse de diols, polyéthers réticulés, et de polyuréthanes sans isocyanate (NIPU). Les synthèses de NIPU réalisées à partir de diamines courtes ou longues (issus de dimer d’acide gras) a permis d’étudier les relations existantes entre le choix des monomères et les températures de transitions vitreuses des matériaux polymères résultant. / In a context of renewable molecules valorization, new molecular architectures and polyols have been developed from sorbitol and various biobased building-blocks with respect to the green chemistry principles. Several polyesters polyol have been synthesized from controlled esterification reactions in bulk conditions. Thanks to the used of variable size diols (C2 to C12) monomers, polyols final viscosity and hydroxyls values were tuned until the obtaining of suitable properties for polyurethanes foams elaborations. Thus, semi-flexible polyurethane foams and rigid polyisocyanurate foams were formulated with fast foaming kinetic profiles (less than 3 min). Rigids polyisocyanurates foams exhibit excellent mechanical and thermal properties, in great agreement with building insulating application requirement. Otherwise, transesterifications reaction involving sorbitol and dimethyl carbonate were studied in order to develop a new bi-functional chemical platform, a bis-cyclocarbonate. Ring opening polymerization and aminolysis reactions were investigated from this chemical platform to the elaboration of cross-linked polyether and non-isocyanate polyurethanes (NIPU). NIPU syntheses were performed with short and long diamines in order to study the relationships between monomers choice and the resulting polymer material temperature of glass transition.

Size effects in out-of-plane bending stiffness of honeycomb cellular materials were studied using analytical mechanics of solids modeling, fabrication of samples and mechanical testing. Analysis predicts a positive size-effect relative to continuum model predictions in the flexure stiffness of a honeycombed beam loaded in out-of-plane bending. A method of determining the magnitude of that effect for several different methods of constructing or assembling square-celled and hexagonal-celled materials, using both single-walled and doubled-walled construction methods is presented. Hexagonal and square-celled honeycombs, with varying volume fractions were fabricated in Nylon 12 using Selective Laser Sintering. The samples were mechanically tested in three-point and four point-bending to measure flexure stiffness. The results from standard three-point flexure tests, did not agree with predictions based on a mechanics of solids model for either square or hexagonal-celled samples. Results for four-point bending agreed with the mechanics of solids model for the square-celled geometries but not for the hexagonal-celled geometries. A closed form solution of an elasticity model for the response of the four-point bending configuration was developed, which allows interpretation of recorded displacement data at two points and allows separation the elastic bending from the localized, elastic/plastic deformation that occurs between the loading rollers and the specimen’s surface. This localized deformation was significant in the materials tested. With this analysis, the four-point bending data agreed well with the mechanics of solids predictions. / text

Superconductors present great potential for weight reduction and increased power delivery when compared to traditional copper power delivery systems, but current systems require cryogenic cooling systems. Traditional superconductor cooling systems consist of helium cooled by helical heat exchangers made of Oxygen Free High thermal Conductivity (OFHC) copper tube. The helium is cooled by bulky heat exchangers consisting of OFHC copper coils wrapped around a cryogenic cooler heat sink for heat transfer into the working fluid. Metal foams have recently been studied in a variety of heat transfer applications, and could greatly reduce the weight of heat exchanger modules in superconductor cooling systems while simultaneously providing increased heat transfer effectiveness. Aluminum and Copper foams have been available for several years, but more recently, graphite foams, such as PocoFoam™, have been developed which have particularly good heat transfer characteristics. Using Computational Fluid Dynamics (CFD) to model a cryogenic heat exchanger application, this study examines the effectiveness and pressure drop of several metal foam heat exchangers, and compares their performance with the traditional helical coil design for superconductor cooling applications. The CFD simulation results show that a heat exchanger with the same heat sink contact area as existing helical heat exchangers weighs up to 95 percent less and can be up to 25 percent more effective, depending on system conditions such as pressure, cryogenic cooler temperature and helium inlet temperature. Aluminum and copper foam heat exchangers had comparable weight to the PocoFoam heat exchanger, but were significantly less effective than the helical or PocoFoam heat exchanger models.

No description available.

The limiting current technique has widely been used to study liquid-solid mass transfer in various reactor configurations. In the present contribution several underlying physical aspects have been investigated in order to improve the design of mass transfer experiments. Experimentally, the significant influence of electrolyte composition and hydrodynamic conditions have been studied and quantified to ensure conditions of high reproducibility. In the course of single phase COMSOL simulations, different electrode configurations have been examined with emphasis on concentration fields and electric current distribution showing a large sensitivity of the experimental configuration on the absolute current values.

Les mousses aqueuses sont des fluides complexes constitués de dispersions concentrées de bulles de gaz dans une solution de tensioactifs. A l'instar d'autres fluides complexes comme les émulsions ou les pâtes, une mousse se comporte comme un solide viscoélastique lorsque la fraction volumique de la phase continue est suffisamment faible pour que l'empilement des bulles soit bloqué. Ses propriétés mécaniques résultent de couplages entre processus se produisant à plusieurs échelles de temps et d'espace : celles des tensioactifs adsorbés aux interfaces liquide-gaz, celles d'une bulle de gaz ou de mouvements collectifs à une échelle mésoscopique. A partir de trois expériences, nous avons mis en évidence l'impact du désordre de leur structure d'une part, et celui des tensioactifs d'autre part, sur les propriétés viscoélastiques des mousses. Nous avons mis au point un rhéomètre oscillatoire qui permet de mesurer la relation contrainte-déformation-fréquence d'une monocouche de bulles confinées entre deux parois planes parallèles tout en contrôlant sa pression osmotique. Nous avons montré que les relaxations de ces mousses de structure modèle sont pilotées par la rhéologie interfaciale de cisaillement que nous avons caractérisée indépendamment. Nous proposons un modèle quantitatif de ce couplage. Dans une deuxième expérience, nous avons sondé la réponse viscoélastique des mousses de structure 3D désordonnées. Nos résultats montrent que selon la rigidité des interfaces, le facteur de perte d'une mousse est décrit par une loi d'échelle en fréquence. Son évolution avec la taille des bulles et la viscosité du liquide permet de déterminer le mécanisme à l'origine de la dissipation. Dans une troisième expérience, Nous avons élaboré des mousses monodisperses de structure 3D ordonnées et de pression osmotique contrôlée. De manière remarquable, la variation de leur facteur de perte en fonction de la fréquence est similaire à celle des mousses désordonnées de même composition chimique. Ces résultats démontrent que le désordre de l'empilement des bulles n'est pas à l'origine des relaxations viscoélastiques linéaires des mousses, comme l'avaient suggéré plusieurs modèles théoriques, et ouvrent la voie à une modélisation quantitative du lien entre la viscoélasticité des interfaces et celle des mousses 3D / Aqueous foams are constituted of concentrated gas bubble dispersions in a surfactant solution. Like other complex fluids, such as emulsions or pastes, foam behaves as a viscoelastic solid if the volume fraction of the continuous phase is sufficiently small for the bubble packing to be jammed. The mechanical properties of the foam are due to couplings between processes at a wide range of time and length scales: The ones of the surfactant molecules that are adsorbed to the gas-liquid interfaces, the ones of the bubbles or collective motions at a mesoscopic scale. On the basis of three experiments, we have evidenced the impact of structural disorder and surfactant properties on foam viscoelasticity. We have constructed an oscillatory rheometer to measure the frequency and strain dependent stress response of a bubble monolayer confined between two parallel plates, subjected to an imposed osmotic pressure. We have shown that the relaxation of these model foams are governed by the interfacial shear rheology which we have probed in independent experiments and, we present a quantitative model of this coupling. In a second experiment, we have probed the viscoelastic response of disordered 3D foams. Our results show that, depending on interfacial rigidity, the mechanical loss factor of a foam is described by a scaling law depending on frequency. Its dependence on bubble size and liquid viscosity helps to determine the origin of the dissipation. In our third experiment, we have produced monodispersed ordered foams, subjected to a controlled osmotic pressure. Remarkably, the frequency scaling of their loss factor is similar to the one of disordered foams of the same chemical composition. These results demonstrate that the linear viscoelastic response of foams is not the consequence of disorder on the bubble scale as suggested by several previous theories, and they thus open the way for quantitative models linking the viscoelasticity of the interfaces to that of 3D foams

Ce travail concerne principalement la détermination des propriétés acoustiques de mousses. Il s’agit d’un projet mené dans le cadre d’une collaboration entre une équipe de physico-chimie des mousses chargée de l’élaboration de matériaux modèles (laboratoire Navier UMR 8205 CNRS) et une équipe d’acousticiens chargée de l’étude de leurs propriétés acoustiques (laboratoire MSME UMR 8208 CNRS). Cette thèse s’articule essentiellement autour de trois parties principales, dont le contenu est résumé ci-dessous. 1) La première partie porte sur la génération de surfaces de réponse par des approximations polynomiales, dans le but de disposer d'un modèle intermédiaire entre le modèle éléments finis micro-macro et la réponse macroscopique. Au lieu d'appeler le modèle éléments finis systématiquement dans un travail d'optimisation, on a recourt à la surface de réponse qui contient l'information associée aux points de calcul éléments finis ainsi que les interpolations correspondantes. Ce manuscrit a été publié dans le journal AAA sous forme de communication rapide. 2) La deuxième partie porte sur la mise au point d'un modèle semi-analytique définit à partir d'une formule disponible pour prédire la perméabilité d'une plaque infinie percée par un trou de surface connue. Ce modèle, utilisé de manière appropriée, permet de calculer la perméabilité de mousses dont la taille de bulles est constante et le taux de fermeture de membranes variable. Des validations numériques par éléments finis et expérimentales sont proposées. L'article a été accepté pour publication dans la revue Physical Review E. 3) La troisième partie, porte sur un calcul éléments finis dans lequel un grand nombre de réalisations sont menées de manière à prendre en compte l'ensemble des combinaisons possibles lorsque on dispose de caractérisation expérimentales fines à l'échelle de la microstructure et que l'on souhaite connaitre la réponse de la mousse avec précision. Le manuscrit est en préparation et la revue visée pour ce dernier manuscrit est le journal Materials and Design. Une introduction et une conclusion générale complètent ces trois parties, et permettent de mettre en perspectives ces contributions par rapport à la littérature existante sur le sujet / This work mainly concerns the determination of the acoustic properties of foams. This is a project carried out as part of a collaboration between a team of physico-chemistry of foams in charge of the development of model materials (Navier laboratory UMR 8205 CNRS) and a team of acousticians responsible for the study of their acoustic properties (MSME laboratory UMR 8208 CNRS). This thesis is structured around three main parts, the content of which is summarized below. 1) The first part deals with the generation of response surfaces by polynomial approximations, in order to have an intermediate model between the micro-macro finite element model and the macroscopic response. Instead of calling the finite element model systematically in an optimization work, we use the response surface that contains the information associated with finite element calculation points and the corresponding interpolations. This manuscript was published in the AAA journal as a fast track publication. 2) The second part focuses on the development of a semi-analytical model defined from an available formula to predict the permeability of a circular orifice in a thin plate. This model, used in an appropriate way, makes it possible to calculate the permeability of foams with a constant bubble size but a tuned membrane content. Numerical validations by finite element computations are proposed. The article has been accepted for publication in the journal Physical Review E. 3) The third part deals with a finite element calculation in which a large number of realizations are carried out in order to take into account all the possible combinations when one has fine experimental characterization at the microstructure scale and that one seek to determine the properties of the foam with precision. The manuscript is in preparation and a possible journal for the publication of this manuscript is the journal Materials and Design. An introduction and a general conclusion complete these three parts, and make it possible to discuss these contributions

L’étude se situe dans le cadre de la recherche de gains de performance de structures d’isolations passives pour l’offshore profond. Le travail proposé a pour support des analyses expérimentales et numériques de tubes revêtus par des matériaux isolants utilisés en eau profonde pour transporter du fluide chaud. Le raboutage des tubes en acier, préalablement revêtus en atelier, nécessite un dégagement du revêtement aux extrémités pour réaliser l'opération d'assemblage (généralement par soudure). La partie dégagée est ensuite recouverte par un nouveau matériau pouvant être appliqué sur site. Ainsi l’isolation de cette partie du tube (Field Joint), qui est soumise à des chargements thermomécaniques en service, doit être optimisée pour assurer une durée de vie compatible avec les contraintes de l’exploitation offshore en eau profonde. Le travail comporte principalement quatre parties : - la modélisation du comportement thermique pour analyser l’évolution en temps et en espace de la température du matériau au cours de la fabrication, de la pose et en service sachant que pour les matériaux d’isolation le comportement mécanique est fortement dépendant de la température,- une partie expérimentale pour l’analyse du comportement des matériaux isolants en fonction de la température et en fonction de la pression hydrostatique qui est le principal chargement mécanique de ces structures en service,- la modélisation du comportement mécanique des isolants,- et une partie modélisation et simulation du comportement en service d'assemblages multi-matériaux de type industriel, avec prise en compte du comportement non-linéaire des constituants. / Ultra deep offshore oil exploitation presents new challenges to offshore engineering and operating companies. Such applications require the use of pipelines with an efficient thermal protection. Passive insulation materials are commonly used to guarantee the thermal performance of the pipes, and syntactic foams are now the preferred material for this application. The mechanical behaviour of such insulation materials is quite complex, associating time-dependent behaviour of polymers with damage behaviour of glass microspheres. In order to allow an optimisation of such systems, while ensuring in-service durability, accurate numerical models of insulation materials are thus required. During the service life in deep water, hydrostatic pressure is the most important mechanical loading of the pipeline, so this study aims to describe the mechanical behaviour of the material under such loading. Using a hyperbaric chamber, the analysis of the evolution of the volumetric strain with time, with respect to the temperature, under different time-evolutions of the applied hydrostatic pressure is presented in this paper. Such experimental results associated with the mechanical response of the material under uniaxial tensile creep tests, allow the development of a thermo-mechanical model, so that representative loadings can be analysed.

Es werden die Strukturbildung und Benetzung zweidimensionaler (2D) Phasen von Langmuir-Monolagen im lokalen thermodynamischen Gleichgewicht untersucht. Eine Langmuir-Monolage ist ein isoliertes 2D System von Surfaktanten an der Wasser/Luft-Grenzfläche, in dem kristalline, flüssigkristalline, flüssige oder gasförmige Phasen auftreten, die sich in Positionsordnung und/oder Orientierungsordnung unterscheiden. Permanente elektrische Dipolmomente der Surfaktanten führen zu einer langreichweitigen repulsiven Selbstwechselwirkung der Monolage und zur Bildung mesoskopischer Strukturen. Es wird ein Wechselwirkungsmodell verwendet, das die Strukturbildung als Wechselspiel kurzreichweitiger Anziehung (nackte Linienspannung) und langreichweitiger Abstoßung (Oberflächenpotential) auf einer Skala Delta beschreibt. Physikalisch trennt Delta die beiden Längenskalen der lang- und kurzreichweitigen Wechselwirkung. In dieser Arbeit werden die thermodynamischen Stabilitätsbedingungen für die Form einer Phasengrenzlinie (Young-Laplace-Gleichung) und Dreiphasenkontaktpunkt (Young-Bedingung) hergeleitet und zur Beschreibung experimenteller Daten genutzt: Die Linienspannung benetzender 2D Tropfen wird mit Hilfe hängender-Tropfen-Tensiometrie gemessen. Die Blasenform und -größe von 2D Schäumen wird theoretisch modelliert und mit experimentellen 2D Schäumen verglichen. Kontaktwinkel werden durch die Anpassung von experimentellen Tropfen mit numerischen Lösungen der Young-Laplace-Gleichung auf Mikrometerskalen gemessen. Das Skalenverhalten des Kontaktwinkels ermöglicht die Bestimmung einer unteren Schranke von Delta. Weiterhin wird diskutiert, inwieweit das Schalten von 2D Benetzungsmodi in biologischen Membranen zur Steuerung der Reaktionskinetik ein Rolle spielen könnte. Hierzu werden Experimente aus unserer Gruppe, die in einer Langmuir-Monolage durchgeführt wurden, herangezogen. <br /> <br /> Abschließend wird die scheinbare Verletzung der Gibbs&prime;schen Phasenregel in Langmuir-Monolagen (nicht-horizontales Plateau der Oberflächendruck-Fläche Isotherme, ausgedehntes Dreiphasengebiet in Einkomponentensystemen) quantitativ untersucht. Eine Verschmutzung der verwendeten Substanzen ist demnach die wahscheinlichste Erklärung, während Finite-Size-Effekte oder der Einfluss der langreichweitigen Elektrostatik die Größenordnung des Effektes nicht beschreiben können. / The present work investigates the structure formation and wetting in two dimensional (2D) Langmuir monolayer phases in local thermodynamic equilibrium. A Langmuir monolayer is an isolated 2D system of surfactants at the air/water interface. It exhibits crystalline, liquid crystalline, liquid and gaseous phases differing in positional and/or orientational order. Permanent electric dipole moments of the surfactants lead to a long range repulsive interaction and to the formation of mesoscopic patterns. An interaction model is used describing the structure formation as a competition between short range attraction (bare line tension) and long range repulsion (surface potentials) on a scale Delta. Delta has the meaning of a dividing length between the short and long range interaction. In the present work the thermodynamic equilibrium conditions for the shape of two phase boundary lines (Young-Laplace equation) and three phase intersection points (Young&prime;s condition) are derived and applied to describe experimental data: The line tension is measured by pendant droplet tensiometry. The bubble shape and size of 2D foams is calculated numerically and compared to experimental foams. Contact angles are measured by fitting numerical solutions of the Young-Laplace equation on micron scale. The scaling behaviour of the contact angle allows to measure a lower limit for Delta. Further it is discussed, whether in biological membranes wetting transitions are a way in order to control reaction kinetics. Studies performed in our group are discussed with respect to this question in the framework of the above mentioned theory.<br /> <br /> Finally the apparent violation of Gibbs&prime; phase rule in Langmuir monolayers (non-horizontal plateau of the surface pressure/area-isotherm, extended three phase coexistence region in one component systems) is investigated quantitatively. It has been found that the most probable explanation are impurities within the system whereas finite size effects or the influence of the long range electrostatics can not explain the order of magnitude of the effect.

Rapid Rotational Foam Molding (RRFM) is a novel patent-pending process that was designed and developed to maximize the synergistic effects resulting from the deliberate combination of extrusion and rotational foam molding and thereby serve as a time-andenergy efficient technology for the manufacture of integral-skin rotationally molded foams of high quality. This thesis presents a thorough study of the scientific and engineering aspects related to the evolution of the RRFM process and its feasibility. This innovative processing technology was assessed and verified through a battery of planned experimental trials conducted utilizing an in-house custom-built industrial-grade lab-scale experimental setup. The experimental trials involved a variety of polypropylene (PP)- based foamable formulations with a chemical blowing agent (CBA) that were compounded and processed by utilizing an extruder and then foamed and injected as a foamed core, instantly, into the cavity of a suitable non-chilled rotationally molded hollow shell made of non-foamed pulverized PP grades. The investigated mold shapes included a cylindrical shaped mold and a rectangular flat shaped mold. The obtained moldings were examined for the quality of the skin surface, the skin-foam interface, and the achieved foam morphologies that were characterized in terms of foam density, average cell size, and average cell density. Optimal processing parameters were successfully determined for three different PP skin-foam formulation combinations. The accomplished reduction in processing time and energy consumption by implementing RRFM were substantial. A variety of processing impediments that hindered the efficiency of the single-charge conventional rotational foam molding practice were resolved by implementing RRFM; these include: the foam/skin invasion into the skin/foam layer of the manufactured article and the premature decomposition of CBA during compounding or subsequent rotational foam molding processing steps. / UOIT