The thesis deals with the processes that occur in the course of the manufacturing of rigid polyurethane-polyisocyanurate (PU-PIR) foams, their properties and technology. It deals above all with principles of foam nucleation and stability. The purpose of understanding these principles is their possible use for improving thermo-insulating properties of the material. The experimental part of the thesis studies the influence of additives and ultrasound on the PU-PIR foam properties. It has been found that low molecular weight compounds with perfluorinated chain leads to decreasing foam cell size and its lower thermal conductivity. The additives mentioned act probably on the surfactants principle by facilitating nucleation and stabilizing growing centres of bubbles. They probably form also part of blowing agents mixture inside the foam cells which cause lowering of thermal conductivity as well. Compounds with similar chemical structure have unique influence on the properties of rigid PU-PIR foams. Further research ought to be focused on cheaper modes of producing perfluorinated compounds.

The behavior of the system consisted by mixture of two different molecular weight hyaluronates and surfactant was investigated. Mixtures were 17 kDa hyaluronate with 1,46 MDa, 73 kDa with 1,46 MDa, 300 kDa with 1,46 MDa, 806 kDa with 1,46 MDa and 1800 kDa with 1,46 MDa. These compounds were always mixed in the weight ratios 70:30, 50:50 and 30:70. As the surfactant cetrimonium bromide and TWEEN 20 were used. Interactions were studied in aqueous solution with different ionic strength. Sudan red was used as hydrophobic dye. In all experimental series with cetrimonium bromide was observed phenomenon of discontinuous separated phases, described as pearls. Samples containing pearls were tested on stability, were dried and rehydrated back, as were also heated in solution. Subsequently, the particle size was measured in the remaining sample after pearls were filtrated. Mixtures of hyaluronate were characterized by measuring the viscosity using rheology microrheology. It was found that these compounds are heterogeneous and each sample point is not the same viscosity.

No description available.

The influence of soil water repellency (WR) on vegetation recovery after a fire is poorly understood. This dissertation presents strategies to broaden opportunities for enhanced post-fire rangeland restoration and monitoring of burned piñon and juniper (P-J) woodlands by: 1) mapping the extent and severity of critical and subcritical WR, 2) determining the influence of WR on soil ecohydrologic properties and revegetation success, and 3) evaluating the suitability of a wetting agent composed of alkylpolyglycoside-ethylene oxide/propylene oxide block copolymers as a post-fire restoration tool for ameliorating the effects of soil WR and increasing seedling establishment. Results indicate that: • Post-fire patterns of soil WR were highly correlated to pre-fire P-J woodland canopy structure. Critical soil WR levels occurred under burned tree canopies while sub-critical WR extended out to approximately two times the canopy radius. At sites where critical soil WR was present, infiltration rate, soil moisture, and vegetation cover were significantly less than at non-hydrophobic sites. These parameters were also reduced in soils with subcritical WR relative to non-hydrophobic soils (albeit to a lesser extent). Aerial photography coupled with feature extraction software and geographic information systems (GIS) proved to be an effective tool for mapping P-J cover and density, and for scaling-up field surveys of soil WR to the fire boundary scale. • Soil WR impairs seed germination and seedling establishment by decreasing soil moisture availability by reducing infiltration, decreasing soil moisture storage capacity, and disconnecting soil surface layers from underlying moisture reserves. Consequently, soil WR appears to be acting as a temporal ecological threshold by impairing establishment of desired species within the first few years after a fire. • Wetting agents can significantly improve ecohydrologic properties required for plant growth by overcoming soil WR; thus, increasing the amount and duration of available water for seed germination and seedling establishment. Success of this technology appears to be the result of the wetting agent increasing soil moisture amount and availability by 1) improving soil infiltration and water holding capacity; and 2) allowing seedling roots to connect to underling soil moisture reserves.

Le reformage à la vapeur couplé à la sorption in-situ d’un composant du milieu réactionnel (sorption-enhanced steam reforming, SESR) est un procédé d’avant-garde qui permet simultanément la production d’hydrogène de très haute pureté et la capture du CO2. L'objectif principal de ce travail est le développement de nouveaux sorbants pour le CO2 applicables à hautes températures et l’étude de leur application dans SESR. Deux nouvelles méthodes de synthèse ont été proposées pour synthétiser du zirconate de lithium (Li2ZrO3), zirconate de sodium (Na2ZrO3) ainsi que des matériaux à base d’oxyde de calcium (CaO), trois catégories de sorbants capables de réagir avec le CO2 à hautes températures. L’application du Li2ZrO3 à la capture du CO2 a démontré une augmentation de l’activité du matériau produit par une nouvelle méthode de synthèse combinant un surfactant et traitement à ultrasons, comparativement au Li2ZrO3 préparé par une méthode avec surfactant seulement (sans ultrasons) ou par la méthode conventionnelle (mélange des composants en phase liquide). Néanmoins, pour des pressions partielles en CO2 inférieures à 0,75 bar, la faible cinétique de sorption du CO2 obtenue par le Li2ZrO3 limite son application au procédé SESR. En considérant l’amélioration des propriétés de sorption obtenue en appliquant la méthode combinée surfactant/ultrasons à la synthèse du Li2ZrO3, la même technique a été aussi appliquée à la synthèse du Na2ZrO3. Des résultats inattendus ont été pourtant obtenus. Le Na2ZrO3 développé par la nouvelle technique a été moins actif durant les cycles sorption/régénération que celui produit par la méthode conventionnelle, de par la faible résistance de sa structure poreuse à de très hautes températures. La nouvelle méthode de synthèse combinée surfactant/ultrasons a été aussi appliquée pour la synthèse de CaO stabilisé par du zirconium (Zr). Un rapport Zr/Ca de 0,303 a été trouvé optimal pour la production d’un sorbant présentant la meilleure stabilité et activité pour la capture de CO2. Dans les conditions sévères d’opération, les résultats ont généralement indiqué une capacité de sorption du CaO stabilisé supérieure à celle du CaO pure. Dans le but de réduire les coûts de production des sorbants, une source moins chère de CaO (calcaire naturel) a été utilisée en combinaison avec une nouvelle méthode de synthèse qui consiste dans l’acidification du calcaire par de l’acide citrique suivie par une calcination en deux étapes (argon et air). Doté d’une structure hautement poreuse, le CaO produit a révélé une stabilité nettement meilleure par rapport au calcaire, ainsi qu’une capacité accrue de sorption du CO2. La même technique de synthèse a été aussi utilisée pour développer plusieurs matériaux à base de CaO stabilisé par divers oxydes métalliques (Al, Zr, Mg et Y), afin d’améliorer la stabilité du sorbant dans les conditions opérationnelles sévères, particulièrement les hautes températures de régénération en présence de CO2. CaO stabilisé par l’aluminium (Al) ou le zirconium (Zr) a démontré une meilleure activité comparativement aux autres matériaux synthétisés, inclusivement dans des conditions sévères d’opération. L’application de ces deux types de sorbants au vaporeformage du méthane (SESMR) a été ensuite étudiée dans un réacteur à lit fixe. Pour minimiser les limitations diffusionnelles, deux matériaux hybrides sorbant-catalyseur ont été développés. NiO-CaO stabilisé par Zr, préparé par la méthode combinée surfactant/ultrasons, dont le contenu en NiO est de 20.5 % (masse) a montré une efficacité dans la production d’hydrogène de 92% lors du premier cycle de reformage, ce qui est remarquablement plus élevée que le rendement d’équilibre en H2 pour le procédé traditionnel de vaporeformage du méthane (SMR) ( 70%). La méthode acidification/calcination en deux étapes a été utilisée pour produire le deuxième matériau hybride (NiO-CaO stabilisé par Al). L’application du matériau contenant 25 % (masse) de NiO a conduit à une efficacité moyenne de production d’hydrogène de 97.3%, démontrant ainsi son grand potentiel pour le SESMR. Les résultats de ce projet de recherche ont clairement démontré que le procédé SESR est une alternative très avantageuse au procédé traditionnel de reformage à la vapeur (sans séparation in-situ de CO2) pour la production d’hydrogène de très haute pureté. Le matériau hybride sorbant-catalyseur NiO-CaO stabilisé par Al a démontré une excellente activité à long terme, en confirmant son potentiel élevé pour application dans le procédé SESMR. / Sorption-enhanced steam reforming (SESR) is a forefront technology to produce H2 clean fuel, which integrates both CO2 capture and H2 production in a single process. The main objective of this work is to develop novel high-temperature CO2 sorbents and to investigate their application in SESR operation. Special attention was given to lithium zirconate (Li2ZrO3), sodium zirconate (Na2ZrO3) and calcium oxide (CaO)-based materials, as most famous high temperature CO2 sorbents, by applying two novel synthesis techniques. The application of Li2ZrO3 in CO2 capture sorption showed an increase in activity of the material prepared by surfactant template/sonication method compared to Li2ZrO3 prepared by simple surfactant template method (without sonication) or conventional wet-mixing route. Nevertheless, porous Li2ZrO3 still suffered from slow kinetics of CO2 sorption at low CO2 partial pressure (below 0.75 bar), which can limit its application for SESMR operation. Taking into consideration the improvement of Li2ZrO3 sorption properties, the same surfactant template/sonication technique was then applied to develop porous Na2ZrO3. The behavior of the new developed Na2ZrO3 was unexpected. The samples prepared by surfactant template/sonication technique were found to be less active than the conventional Na2ZrO3 during cyclic operation, due to the low resistivity of the pore structure at the very high temperature treatment required for calcination. The same surfactant template/sonication was also applied to develop Zr-stabilized CaO sorbents. An optimum Zr/Ca ratio of 0.303 was found to maximize the stability and CO2 capture activity of the proposed Zr-stabilized CaO sorbent. The results generally showed a better CO2 capture ability of Zr-stabilized CaO sorbent in comparison with pure CaO in severe cyclic operating conditions. With the purpose of reducing the cost of sorbent production, a cheaper source of CaO (natural limestone) was also considered and a novel synthesis technique (limestone acidification by citric acid followed by two-step calcination (in Ar and air atmospheres)) was applied in order to prepare highly porous CaO structure with unique CO2 capture ability. The results revealed a much better stability and CO2 sorption activity of the developed sorbent compared to natural limestone. The same technique was employed to develop a number of metal oxide (Al, Zr, Mg and Y)-stabilized CaO sorbents in order to enhance sorbent stability in severe operating conditions, i.e., high temperature regeneration in the presence of CO2. Al and Zr-stabilized CaO showed the best activity during both mild and severe operating conditions. The performance of the developed CO2 sorbents providing the best performance in CO2 capture (Zr-stabilized and Al-stabilized CaO) were then investigated experimentally in the sorption enhanced steam methane reforming (SESMR) using a fixed-bed reactor. To minimize the diffusional limitations, a hybrid catalyst-sorbent was developed for both sorbents. The application of Zr-stabilized CaO-nickel hybrid catalyst with 20.5 wt% NiO loading, prepared by surfactant-template/sonication method, resulted in 92% H2 production efficiency for the initial SESMR cycle, which is remarkably higher than traditional steam methane reforming (SMR) equilibrium H2 yield (70 %). The second developed hybrid sorbent-catalyst (Al-stabilized CaO-NiO) was prepared using limestone acidification coupled with two-step calcination technique. The long-term application of the hybrid catalyst containing 25 wt% NiO led to an average H2 production efficiency of 97.3%, proving its high efficiency in the SESMR process. In summary, the results of this thesis show that the SESR process is as an efficient alternative of traditional steam reforming for production of highly pure H2. The Al-stabilized CaO-NiO hybrid sorbent-catalyst showed an excellent activity over long-term operation, thus confirming its very high potential for use in the SESMR process.

No description available.

Cellulose is the most abundant biopolymer on Earth as it is found in every plant cell wall; therefore, it represents one of the most promising natural resources for the fabrication of sustainable materials. In plants, cellulose is mainly used for structural integrity, however, some species organise cellulose in helicoidal nano-architectures generating strong iridescent colours. Recent research has shown that cellulose nanocrystals, CNCs, isolated from natural fibres, can spontaneously self-assemble into architectures that resemble the one producing colouration in plants. Therefore, CNCs are an ideal candidate for the development of new photonic materials that can find use to substitute conventional pigments, which are often harmful to humans and to the environment. However, various obstacles still prevent a widespread use of cellulose-based photonic structures. For instance, while the CNC films can display a wide range of colours, a precise control of the optical appearance is still difficult to achieve. The intrinsic low thermal stability and brittleness of cellulose-based films strongly limit their use as photonic pigments at the industrial scale. Moreover, it is challenging to integrate them into composites to obtain further functionality while preserving their optical response. In this thesis, I present a series of research contributions that make progress towards addressing these challenges. First, I use an external magnetic field to tune the CNC films scattering response. Then, I demonstrate how it is possible to tailor the optical appearance and the mechanical properties of the films as well as to enhance their functionality, by combining CNCs with other polymers. Finally, I study the thermal properties of CNC films to improve the retention of the helicoidal arrangement at high temperatures and to explore the potential use of this material in industrial fabrication processes, such as hot-melt extrusion.

Depuis plusieurs décennies, une importante activité scientifique se concentre sur la description numérique, théorique ou expérimentale de l'hydrodynamique des écoulements multiphasiques. Ces écoulements sont caractérisés par l'existence d'interfaces, et d'une force à l'interface, la tension superficielle, séparant généralement deux fluides non miscibles. Un cas d'étude dans ce contexte est le problème du drainage d'une unique goutte dans une phase continue, l'ensemble étant soumis à la gravité. Ce système fait apparaître des écoulements récemment décrits pour une goutte d'eau dans l'huile de paraffine. Ce système constitue également un modèle simple pour l'étude des propriétés aux interfaces, Mais d'un point de vue numérique, se pose alors le problème de la stabilité des algorithmes pouvant être utilisés. Les effets aux interfaces impliquent en effet des domaines spatiaux très limités dans lesquels les grandeurs physiques entre les deux fluides sont discontinues. D'importants artéfacts numériques peuvent alors être générés dans les simulations et faire perdre la richesse de la physico-chimie du système considéré. Le problème de la simulation d'écoulements multiphasiques intéresse aussi bien le monde académique que le monde industriel. L'objectif de ce travail de thèse est donc d'implémenter les techniques numériques les plus récentes et de développer un code pour permettre la simulation de l'hydrodynamique de systèmes dispersés. Pour parvenir à ce but, il reste encore des problèmes algorithmiques importants à résoudre comme la prise en compte des effets thermocapillaires et thermosolutaux. Ces deux derniers points sont l'objet de cette thèse. / For several decades, an important scientific activity has focused on the numerical, theoretical and experimental hydrodynamics of drops. This work presents numerical results of a single droplet in the gravity field and in non-isothermal conditions. The simulation such a multiphase system is important in both academic and industrial world. This is particularly the case in the field of emulsions, wetting problems and evaporation. To achieve this goal, there are still important algorithmic problems due to the free moving interfaces and the description of capillary effects. Here, a Volume of Fluid technique has been implemented with high order temporal and spatial schemes to preserve the sharpness of the drop interface. The system under consideration is a simplified model consisting in a single water droplet in a continuous paraffin oil phase. These liquids are immiscible and non-compressible and the overall evolution is unsteady. Capillary contributions such as temperature and surfactant dependent surface tension are fully accounted for. This presentation is aimed to show the capabilities of VOF techniques for the simulations of unsteady multiphase systems in non-isothermal configurations. The role of the droplet initial position and temperature field is described with good numerical stability. There are still important problems remaining in the simulation of free interface systems with such a technique. Spurious currents induced by the description of capillarity can in particular come into play. But these latter can be controlled once the droplet average velocity due to drainage becomes large enough.

No description available.

No description available.