Sustainable desalination technologies are the smart solution for producing fresh water and preserve the environment and energy by using sustainable renewable energy sources. Membrane distillation (MD) is an emerging technology which can be driven by renewable energy. It is an innovative method for desalinating seawater and brackish water with high quality production, and the gratitude is to its interesting potentials. MD includes a transfer of water vapor from a feed solution to a permeate solution through a micro-porous hydrophobic membrane, rejecting other non-volatile constituents present in the influent water. The process is driven by the temperature difference along the membrane boundaries. Different control applications and supervision techniques would improve the performance and the efficiency of the MD process, however controlling the MD process requires comprehensive mathematical model for the distributed heat transfer mechanisms inside the process. Our objective is to propose a dynamic mathematical model that accounts for the time evolution of the involved heat transfer mechanisms in the process, and to be capable of hosting intermittent energy supplies, besides managing the production rate of the process, and optimizing its energy consumption. Therefore, we propose the 2D Advection-Diffusion Equation model to account for the heat diffusion and the heat convection mechanisms inside the process. Furthermore, experimental validations have proved high agreement between model simulations and experiments with less than 5% relative error. Enhancing the MD production is an anticipated goal, therefore, two main control strategies are proposed. Consequently, we propose a nonlinear controller for a semi-discretized version of the dynamic model to achieve an asymptotic tracking for a desired temperature difference. Similarly, an observer-based feedback control is used to track sufficient temperature difference for better productivity. The second control strategy seeks for optimizing the trade-o between the maximum permeate flux production for a given set of inlet temperatures of the feed and the permeate solutions, and the minimum of the energy consumed by the pump ow rates of the feed and the permeate solutions. Accordingly, Extremum Seeking Control is proposed for this optimization, where the pump flow rates of the feed and the permeate solutions are the manipulated control input.

Due to the limited number of approved antioxidants for food applications, several alternative strategies to improve antioxidant performance have been developed by focusing on synergistic antioxidant interactions. Susceptibility to lipid oxidation in food systems is the result of the summation of antioxidative and prooxidative mechanisms. Understanding the sometimes paradoxical behavior of antioxidants and prooxidants is a vital key to design synergistic antioxidant systems suitable for particular foods. This research focused on 3 main strategies to improve the performance of antioxidant activity in oil-in-water emulsions. The first part of this research has been focused on inhibition of lipid oxidation by a combination of the modification of liposomal surfaces by chitosan-coating techniques along with addition of rosmarinic acid esters of varying polarity. Repelling metal ions away from the interface of positively charged liposomes can inhibit lipid oxidation (induced by Fe2+), and also reduce antioxidant loss by Fe3+ reduction. As a result, lipid oxidation can be inhibited synergistically because of a reduction in the prooxidant activity of iron. Second, understanding non-linear antioxidant behavior (the cut-off effect) of antioxidant esters in oil-in-water (O/W) emulsions was also studied to determine how the distributions and locations of antioxidants impacted their antioxidant activity. Antioxidant activity of rosmarinic acid was improved by esterification with alkyl chain lengths between 4 to 12 carbons due to increased ability to partitioning at the interface in oil-in-water emulsions. Surfactant micelles which could increase or decreased the concentration of the antioxidants at the emulsion droplet interface altered antioxidant activity. In the last part of this research, rosmarinic acid and its esters were found to be an excellent tool for studying how antioxidant location could impact its ability to interact with α-tocopherol in O/W emulsions. Synergistic, additive, and antagonistic effects were observed in the combinations between the rosmarinate esters with α-tocopherol. Increases in alkyl chain lengths of rosmarinic acid have influenced both the partitioning of the rosmarinate esters as well as their ability to they interact with α-tocopherol at the interface of oil-in-water emulsions. Fluorescence quenching and EPR studies showed that water soluble rosmarinic acid (R0) exhibited more interactions with á-tocopherol than any of the esters (R4-R20). Synergistic antioxidant interactions between rosmarinic acid and α-tocopherol could not be explained by electron transfer mechanisms, but formation of caffeic acid from rosmarinic acid. Due to the thermodynamic infeasibility and the fact that increases in α-tocopherol degradation rates, α-tocopherol could not be regenerated efficiently by rosmarinic acid. This formation of caffeic acid was proposed to be responsible of the synergistic activity of R0 and α-tocopherol since the formation of an additional antioxidant could further increase the oxidative stability of the emulsion.

No description available.

L'extraction de biomolécules à partir de ressources renouvelables devient l'un des thèmes clés dans les domaines de la biotechnologie, de la cosmétologie et de la pharmacie. Pour minimiser la consommation de solvant organique et augmenter l'efficacité, l'extraction avec des mélanges eau/alcool semble être une approche prometteuse. De plus, des étapes supplémentaires de purification et de concentration sont généralement nécessaires pour enrichir le milieu avec les molécules cibles. La nanofiltration (NF) est une technique de séparation idéale et durable pour de telles opérations car elle est propre, sobre et sûre. Il existe néanmoins peu de littérature concernant la NF dans ces mélanges eau/éthanol. Cette étude vise à mieux comprendre les mécanismes de transfert qui régissent la sélectivité dans ces milieux. Dans un premier temps une étude fondamentale est réalisée sur la NF dans des mélanges eau/ alcool seuls ou en présence de solutés neutres et/ou chargés. Les résultats obtenus montrent que lorsque la teneur en alcool augmente, la membrane gonfle, le rayon des pores augmente mais la résistance intrinsèque reste constante. Les mécanismes de transfert bien connus en milieux aqueux (exclusion stérique, interaction électrostatique, interaction diélectique) et en milieux organiques (interactions hydrophobes, affinité soluté-membrane-solvant) sont tous présents dans des mélanges eau/alcool mais leur intensité relative semble être différente. Différents modèles (Spiegler-Kedem & Film, Hydrodynamique & Film, Solution-Diffusion & Film, Pore-Flow & Film, Steric Electric and Dielectric Exclusion) ont été utilisés pour modéliser les rétentions et estimer les paramètres de transfert. / The extraction of bio-molecules from renewable resources is emerging as one of a key topics in the fields of biotechnology, cosmetology and pharmacy. To minimize the organic solvent consumption, as well as to increase the efficiency, extraction by water/alcohol mixtures appears to be a promising approach. Moreover, additional purification and concentration steps are generally required to enrich the medium with the target molecules. Nanofiltration is a de-facto separation technique for such operations because it is clean, sober and safe. Unfortunately, there is few literature on the transfer of water/ethanol mixtures regarding nanofiltration. This study aims to better understand the transfer mechanisms that govern selectivity in these media. At the first step, a fundamental study is realized on nanofiltration in water/alcohol mixtures alone or with the presence of neutral or charged solutes. The obtained results show that when the alcohol content increases, the membrane is swelling, the pore radius increases but the intrinsic resistance is still constant. The well-known transfer mechanisms in aqueous media (steric exclusion, electric interaction, dielectric interaction) and in organic media (hydrophobic interaction, affinity solute-membrane-solvent) are all present in the water/alcohol mixtures, but relative intensity appears to be different. Different models (Spiegler-Kedem & Film, Hydrodynamics & Film, Solution-Diffusion & Film, Pore-Flow & Film, Electric Steric and Dielectric Exclusion) were used to model the retentions and estimate the transfer parameters.

L’étude réalisée lors de ce travail de thèse porte sur l’évaluation de l'impact de l’agglomération Marseillaise sur le milieu côtier à travers la quantification des éléments traces métalliques (ETM) et du carbone organique. Sur le littoral méditerranéen français, Marseille représente la plus grande agglomération (~ 1.7M Ha) et possède la station d’épuration (STEP) enterrée la plus grande d’Europe (capacité de 1.62M équivalent-habitants), avec une façade directement ouverte sur la Méditerranée. L’impact de cette zone urbaine et industrialisée (flux brut) sur la zone côtière reste mal compris, de par la multiplicité des sources (apports directs(rivières/effluents) vs. apports diffus (friches industrielles côtières, aérosols, ...)) en partie contrôlée par le climat. Il en est de même des mécanismes de transfert des contaminants conditionnant leur devenir dans le milieu marin (flux nets vers le large). Dans ce contexte, différentes campagnes de prélèvements d’eau et de sédiments ont été mises en oeuvre sous des conditions climatiques contrastées (temps sec vs. pluie) dans les rivières ainsi qu'en mer, le long d’un transect allant de la côte à plus de 2 km au large des rejets. Les objectifs de cette étude visaient à déterminer les sources de contaminants au milieu côtier et à comprendre leurs mécanismes de transfert et leur devenir en mer. Par temps sec, les résultats obtenus ont montré que la dynamique du système est principalement contrôlée par les rejets de la STEP qui, par exemple, est responsable à plus de 75% des apports en Ag, Cu ou Pb au milieu côtier. Une fois en mer, les différents ETM analysés présentent un profil non conservatif, dû à un fractionnement dissous/particulaire hors équilibre dans les émissaires associé à un relargage rapide au début du gradient de salinité. Ces résultats ont été confirmés par une expérience de remobilisation réalisée au laboratoire permettant de mieux comprendre la cinétique de désorption des ETM. Dans ces conditions, il a été démontré qu'il était indispensable de filtrersur le terrain les échantillons pour ne pas sous-estimer la fraction dissoute des ETM. Par temps de pluie, le suivi des apports au cours d'une crue a montré la très grande réactivité du système, typique de rivières côtières. La majorité des ETM, transportés principalement sous forme particulaire, subissent une fois en mer des processus de désorption avec des cinétiques plus lentes et à des salinités plus importantes que par temps sec. Ces différences sont probablement liées à la nature des particules, urbaines et très organiques par temps sec, plutôt terrigène et inorganiques par temps de pluie. Enfin, une expérience de vitesse de chute des particules transitant dans le système par temps sec et de pluie a été développée au laboratoire. Elle a permis de caractériser les particules étudiées par des paramètres physico-chimiques intégrables au modèle hydro-sédimentaire de l'IFREMER, permettant de mieux évaluer le devenir des particules en zone côtière. / The aim of this PhD was to evaluate the impact from Marseille agglomeration on thecoastal area, using trace metals and organic carbon quantification. On the French Mediterraneancoast, Marseille is the largest agglomeration (~1.7M inhabitants), located directly on coast andhave the biggest European underground wastewater treatment plan (WWTP, 1.62M eq). Theimpact of this urbanized and industrialized area on the coastal zone (bulk fluxes) remainsmisunderstood, because of the multiplicity of contaminant sources (direct inputs(rivers/effluents) vs. diffusive ones (coastal industrial wasteland, aerosols, …)) partlycontrolled by climatic conditions. Similarly, the transfer mechanisms of contaminants thatcontrol their fate to the open sea (net fluxes) have to be studied. In such context, numerouswater and sediment sampling campaigns were performed during contrasted climatic conditions(baseflow vs. flood) in the tributaries and along a 2km coastal-offshore transect in front of theoutputs. The main objectives of this study were to determine contaminants sources, transfermechanisms and fate in the coastal zone. During baseflow conditions, results have shown thatthe system dynamic is mainly controlled by the WWTP inputs, that are for instance the maincontributor (>75%) of Ag, Cu or Pb inputs to the coastal area. When discharged to the sea, thestudied trace metals presented non-conservative behaviours, consecutive to adissolved/particulate fractionation out of equilibrium in the outlets associated to fastremobilization at the beginning of the salinity gradient. These results were confirmed by labremobilization experiments allowing to better understand the desorption kinetics of tracemetals. Under such conditions, it was demonstrated that on-field filtration is a prerequisite toavoid under-estimation of the dissolved fraction of trace metals. The monitoring of a flood eventduring a rainy period has shown the high reactivity of the studied system, a peculiarity ofMediterraneean coastal rivers. Most of the studied trace metals, mainly brought in theparticulate fraction, suffer desorption processes when discharged to the sea, a processcharacterized by kinetics slower and effective at higher salinity in comparison to baseflowinputs. These differences are most probably linked to the nature of particles being urban andorganic during baseflow, mostly terrigeneous and inorganic during flood. Finally, a settling rateexperiment was designed in the lab in order to evaluate the physical and chemical characteristicsof representative particles. The obtained parameters were integrated in the 3D hydrodynamicand sediment transport model of IFREMER allowing to better evaluate the fate of pollutedparticles in the coastal area.

Content: Leather is a fairly durable and flexible material created by tanning animal rawhides and can be found in many household and personal products. However, ensuring that the product endures attack from the environmental elements that contribute to its wear and tear is the key concern of the general consumer. Animal rawhides are soft collagenous connective tissues. The most important function of collagen is a mechanical one - to withstand loads acting on the leather material. The purpose of this paper is to show how findings from recent studies on the mechanics of collagen in connective tissues lend to the goal of structural biologists to establish a complete understanding of the functional significance of collagen in connective tissues. In particular, 28 different types of collagen have been identified - about 90% being type 1 collagen - in the human body. Most types of collagen participate in higher-order assemblies such as networks, filaments, microfibrils, fibrils, fibres/fascicles. These assemblies collectively form a hierarchical architecture in the tissue from the molecular level to the macroscopic level. A complete understanding the functional significance of collagen in connective tissues could direct the development of new technology, e.g. leather design and production. In this paper, I shall discuss findings related to the higher-order assemblies. The conventional understanding of the collagenous fibre-like structures - embedded in a hydrated ground substance - in connective tissue finds an analogy to engineering fibres reinforcing composite materials such as carbon fibre reinforced polymer composites. The macroscopic stress- strain response of the connective tissue to external loads acting on it is consistent with fibre composite behaviour. A structure-mechanical framework, underpinning the hierarchical architecture of the connective tissue, is proposed to explain this mechanical response of the tissue. By integrating models specific to the different levels of the tissue to enable better understanding of the macroscopic nature of the tissue, the framework serves as a representation of reality for guiding further research, especially for the purpose of exploring hypotheses and revealing properties for which only sparse (or no observational data) is available. This paper ends with a discussion on the prospect and challenges for future studies on collagen in connective tissues. Take-Away: A fresh look at the degree of collagen fibril alignment in tissue Rethinking the mechanics of cross-linking between fibrils Interfibrillar mechanics is governed by plastic stress transfer Influence of fibril diameter on interfibrillar stress transfer

<p>Secondary cooling during continuous casting is a delicate process because the cooling rate of water spray directly affects the slab surface and internal quality. Undercooling may lead to slab surface bulging or even breakout, whereas overcooling can cause deformation and crack of slabs due to excessive thermal residual stresses and strains. Any slab which does not meet the required quality will be downgraded or scrapped and remelted. In order to remain competitive and continuously produce high-quality and high-strength steel at the maximum production rate, the secondary cooling process must be carefully designed and controlled. Efficient and uniform heat removal without deforming or crack the slab is a significant challenge during secondary cooling. In the meantime, the on-site thermal measurement techniques are limited due to the harsh environment. In contrast, experimental measurements are only valid for the tested conditions, and the measurement process is not only labor-intensive, but the result might be inapplicable when changes in the process occur. On the other hand, the high-performance computing (HPC)-powered computational fluid dynamics (CFD) approach has become a powerful tool to gain insights into complex fluid flow and heat transfer problems. Yet, few successful numerical models for heat transfer phenomena during secondary cooling have been reported, primarily due to complex phenomena. </p> <p> </p> <p>Therefore, the current study has proposed two three-dimensional continuum numerical models and a three-step coupling procedure for the transport of mass, momentum, and energy during the secondary cooling process. The first numerical model features the simulation of water spray impingement heat and mass transfer on the surface of a moving slab considering atomization, droplet dispersion, droplet-air interaction, droplet-droplet interaction, droplet-wall impingement, the effect of vapor film, and droplet boiling. The model has been validated against five benchmark experiments in terms of droplet size prior to impingement, droplet impingement pressure, and heat transfer coefficient (HTC) on the slab surface. The validated model has been applied to a series of numerical simulations to investigate the effects of spray nozzle type, spray flow rate, standoff distance, spray direction, casting speed, nozzle-to-nozzle distance, row-to-row distance, arrangement of nozzles, roll and roll pitch, spray angle, spray water temperature, slab surface temperature, and spray cooling on the narrow face. Furthermore, the simulation results have been used to generate a mathematically simple HTC correlation, expressed as a function of nine essential operating parameters. A graphic user interface (GUI) has been developed to facilitate the application of correlations. The calculated two-dimensional HTC distribution is stored in the universal comma-separated values (csv) format, and it can be directly applied as a boundary condition to on-site off-line/on-line solidification calculation at steel mills. The proposed numerical model and the generic methodology for HTC correlations should benefit the steel industry by expediting the development process of HTC correlations, achieving real-time dynamic spray cooling control, supporting nozzle selection, troubleshooting malfunctioning nozzles, and can further improve the accuracy of the existing casting control systems.</p> <p> </p> <p>In the second numerical model, the volume-averaged Enthalpy-Porosity method has been extended to include the slurry effect at low solid fractions through a switching function. With the HTC distribution on the slab surface as the thermal boundary condition, the model has been used to investigate the fluid flow, heat transfer, and solidification inside a slab during the secondary cooling process. The model has been validated against the analytical solution for a stationary thin solidifying body and the simulation for a moving thin solidifying body. The effects of secondary dendrite arm spacing, critical solid fraction, crystal constant, switching function constant, cooling rate, rolls, nozzle-to-nozzle distance, and arrangement of nozzles have been evaluated using the validated model. In addition, <a>the solidification model has been coupled with the predictions from the HTC correlations, and the results have demonstrated the availability of the correlations other than on-site continuous casting control. </a>Moreover, the model, along with the three-step coupling procedure, has been applied to simulate the initial solidification process in continuous casting, where a sufficient cooling rate is required to maintain a proper solidification rate. Otherwise, bulging or breakout might occur. The prediction is in good agreement with the measured shell thickness, which was obtained from a breakout incident. With the help of HPC, such comprehensive simulations will continue to serve as a powerful tool for troubleshooting and optimization.</p>

Les matériaux polymères sont à l'heure actuelle peu considérés dans le vaste domaine des micro et nano technologies. Ils présentent toutefois certaines propriétés remarquables en comparaison des matériaux traditionnels de la microélectronique. Par exemple leur déformabilité et leur légèreté permettent d'envisager des fonctions de supports flexibles pour des composants électroniques. Par ailleurs, ils offrent des solutions d'assemblage de matériaux de diverses natures. Cette étude porte précisément sur ces deux thématiques. En premier lieu, nous avons étudié les mécanismes de collage impliqués dans l'assemblage de substrats de type silicium par une couche de polymère. D'autre part, nous avons proposé des modèles de mécanisme de transfert de films monocristallins sur polymère. Les propriétés mécaniques des matériaux considérés, principalement du silicium monocristallin et des polymères de type vitreux et caoutchoutique, ainsi que leurs épaisseurs, peuvent varier sur plusieurs ordres de grandeur selon la configuration considérée. L'originalité de l'étude est de déterminer et d'aborder des configurations expérimentalement favorables, par des modèles mécaniques simples, élaborés à partir de lois d'échelle. Nous avons proposé, dans un premier temps, ces modèles pour expliquer des résultats liés à des configurations particulières et ainsi démontrer la pertinence de cette approche. Le cœur de notre étude porte sur le transfert de films monocristallins, aussi fins qu'une centaine de nanomètres d'épaisseur, sur polymère par adaptation du procédé Smart-CutTM (transfert par implantation ionique et fracture). En comparaison d'une configuration standard de cette technologie, nous avons notamment étudié l'impact des propriétés mécaniques propres aux polymères (de types vitreux ou caoutchoutique). Les méthodes en loi d'échelle nous ont ainsi permis de proposer des mécanismes de transfert, de l'échelle du nanomètre jusqu'à la fracture macroscopique. Nous avons également exposé un exemple d'application concret par la réalisation d'objets microélectroniques modèles sur et dans un film monocristallin de silicium. La structure, composée d'un film de quelques micromètres d'épaisseur supporté par un polymère, constitue ainsi une structure flexible d'un point de vue mécanique. / Polymers are little considered at the moment, in the wide domain of micro- and nano- technologies. They present however certain remarkable properties by comparison with the materials used in microelectronics. For example their flexibility and their lightness allow thinking to polymers as flexible supports for microelectronic components. Besides, they offer solutions for assembling various materials.This study concerns exactly these two items. First of all, we studied bonding mechanisms implied in the assembly of silicon wafers via polymer layers. Then we proposed models for mechanism of single-crystalline layer transfers onto polymers. The mechanical properties of the considered materials (mainly single-crystalline silicon and glassy or rubber polymers) as well as their thicknesses can vary on several orders of magnitude according to the application.The originality of the study is to determine favorable experimental configurations, by simple mechanical models developed from scale laws, and to realize demonstrators. The heart of our study concerns the transfer of single-crystalline layers as thin as about hundred nanometers onto polymers by tuning of the Smart-CutTM technology (based on ion implantation and splitting for transfer). By comparison with a standard configuration of this technology, we studied the impact of the specific mechanical properties of polymers (glassy or rubber types). The methods in scale laws allowed us proposing transfer mechanisms, from the nanometer scale up to the macroscopic one. Finally we reported on a realization of micro-technology devices, made in and on single-crystalline thin silicon membranes. The stacked structures, consisting in silicon membranes thick of a few micrometers supported by polymer films, may be considered as very flexible structures.

This diploma thesis is focused on the experimental determination of thermal resistance of the gloves and their combination in the layering system. The measurement was based on procedure specified in the standard ČSN EN 511 by means of thermal manikin. The thesis begins with the description of heat transfer mechanisms, description of glove materials and measurement methodology. The body of paper consists of the measured data analysis and equation design for determination of the glove layering system thermal resistance. At the end of the thesis, these equations are evaluated and it has been shown, that the thermal resistance of glove layering system cannot be precisely determined by the calculation, and it is necessary to measure the whole three-layer system.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第21357号 / 工博第4516号 / 新制||工||1703(附属図書館) / 京都大学大学院工学研究科都市社会工学専攻 / (主査)教授 大津 宏康, 准教授 PIPATPONGSA Thirapong, 教授 三村 衛 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM