L’objectif principal de ce travail a été d’étudier le potentiel de mousses alvéolaires tridimensionnelles en carbure de silicium de forme béta (β-SiC) comme support de photocatalyseur, dans le but de mettre au point des réacteurs photocatalytiques structurés pour le traitement de l’air. Ces mousses alvéolaires de β-SiC de surface spécifique moyenne et de porosité très ouverte sont obtenues par la synthèse dite à mémoire de forme (Shape Memory Synthesis), consistant en la carburation contrôlée d’une mousse alvéolaire de polyuréthane préformée. Une étude de la dégradation de trois polluants sur des films minces en mode de lit léchant (la méthyléthylcétone, l’ammoniac et le sulfure d’hydrogène) a tout d’abord permis de sélectionner trois photocatalyseurs d’intérêt parmi six références commerciales avant d’être immobilisés sur les mousses de β-SiC. Après une étape d’optimisation en termes de taille d’alvéoles, de nature et quantité de photocatalyseur, le média photocatalytique TiO2/mousses de β-SiC a été caractérisé et ses performances comparées en mode mono-passage ainsi qu’en mode de recirculation du flux dans une enceinte de 2 m3, à celles d’un film mince de TiO2 et d’un média photocatalytique commercial de référence. Le média photocatalytique TiO2/mousses de β-SiC présente des performances nettement améliorées par rapport à celles du média référent. Les mousses jouent un rôle de mélangeur statique et permettent une meilleure utilisation du volume du réacteur, en augmentation la densité de photocatalyseur par unité de volume tout en maintenant une illumination du cœur du réacteur acceptable ainsi que des pertes de charge très limitées. / The main objective of this work was to study the potential of three-dimension beta silicon carbide (β-SiC) alveolar foams for use as photocatalyst support, targeting the implementation of structured photocatalytic reactors for air treatment. Medium surface area β-SiC alveolar foams were synthesized according to the Shape Memory Synthesis concept, consisting in the controlled carburization of a preshaped polyurethane foam. First, the degradation of three model pollutants (methylethylketone, ammonia and hydrogen sulfide) was performed over TiO2 thin layers in a flow-through reactor for selecting three photocatalysts of interest – Hombikat UV100, PC500 and P25 TiO2 – among six commercial standards. The powderly photocatalysts were further immobilized onto β-SiC foams. After an optimization step in terms of mean cell size, light transmission, photocatalyst nature and weight content as well as of the immobilization method, the TiO2/β-SiC foam photocatalytic media was characterized and its photocatalytic behaviour was compared in a single-pass mode as well as in a recirulation mode inside a 2 m3 chamber, to those obtained on a TiO2 thin layer and with a well-known commercial photocatalytic felt media made from quartz fibers supporting sol-gel TiO2. The photocatalytic media elaborated with β-SiC alveolar foams exhibited superior performances compared to that of the commercial felt standard. The foams acted as static mixing within the reactor and allowed a more efficient use of the reactor volume, by increasing the photocatalyst density per reactor volume unit, while maintaining however a suitable illumination within the reactor core as well as very low pressure drops.

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The major challenge associated with renewable-energy systems especially solar, is the supply intermittency. One effective solution is to incorporate thermal energy storage components utilizing phase change materials (PCMs). These materials have the potential to store large amounts of energy in relatively small volumes and within nearly an isothermal storage process. The primary drawback of today’s PCMs is that their low thermal conductivity values critically limit their energy storage applications. Also, this grossly reduces the melting/ solidification rates, thus making the system response time to be too long. So, the application of heat transfer enhancement is very important. To improve the PCM storage performance, an efficient performing containment vessel (triplex-tube) along with applications of various heat transfer enhancement techniques was investigated. The techniques were; (i) dispersion of solid nanoparticles, (ii) incorporation of metal foam with nanoparticle dispersion, and (iii) insertion of longitudinal fins with nanoparticle dispersion. Validated simulation models were developed to examine the effects of implementing these techniques on the PCM phase-change rate during the energy storage and recovery modes. The results are presented with detailed model description, analysis, and conclusions. Results show that the use of nanoparticles with metal foam or fins is more efficient than using nanoparticles alone within the same volume usage. Also, employing metal foam or fins alone results in much better improvement for the same system volume.

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京都大学 / 新制・課程博士 / 博士(工学) / 甲第23930号 / 工博第5017号 / 新制||工||1783(附属図書館) / 京都大学大学院工学研究科化学工学専攻 / (主査)教授 大嶋 正裕, 教授 山子 茂, 教授 佐野 紀彰 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

Traditionally geothermal energy utilizes naturally occurring steam or hot water trapped in permeable rock formations through naturally occurring extraction wells or by implementing the hydraulic fracturing process by fracturing rock formations with water-based fracturing fluids. In contrast, in Enhanced Geothermal System (EGS) hydraulic fracturing process is utilized to create new or reopen existing fractures by injecting high-pressure fluid into deep Hot Dry Rocks (HDR) under carefully controlled conditions. Fracturing fluids are usually water-based that utilize an immense quantity of water. In EGS, they are essential for conducting hydraulic fracturing which bring the concern of technical approach and environmental impact. Thus, an alternative approach is to use waterless fracturing technologies, such as foam-based fracturing fluid. Foams are a complex mixture of the liquid and gaseous phases, where the liquid phase act as an ambient phase and gas is the dispersed phase. Foam fracturing fluids offer potential advantage over conventional water-based fracturing fluids, including reduced water consumption and environmental impact. Although foam-based fracturing has shown promising results in oil and gas industries, its feasibility has not been demonstrated in EGS conditions that usually involve high temperature and high pressures. One potential barrier to utilizing foam as fracturing fluid in EGS applications is that foams are thermodynamically unstable and will become more unstable with increasing temperature due to phenomena such as liquid drainage, bubble coarsening, and coalescence. Therefore, it is essential to stabilize foam fluids at high temperatures for EGS related applications such as fracking of HDRs. This project aims to evaluate the thermodynamic behavior of foams at high temperature and high pressure conditions closely resembling the geothermal environment. In this research, foam behavior was categorized as foam stability based on its half-life, i.e., the time taken by the foam to decrease to 50% of its original height. A laboratory apparatus was constructed to evaluate the foam half-life for a temperature range of room temperature to 200°C and a pressure range of ambient pressure to > 1000 psi. Two types of dispersed/gaseous phases, nitrogen gas (N2) and carbon dioxide gas (CO2), were investigated. Four different types of commercial foaming agents/surfactants with various concentrations were tested, including alfa olefin sulfonate (AOS), sodium dodecyl sulfonate (SDS), TergitolTM (NP – 40), and cetyltrimethylammonium chloride (CTAC). Moreover, five stabilizing agents, guar gum, bentonite clay, crosslinker, silicon dioxide nanoparticles (SiO2), and graphene oxide dispersions (GO), were also added to the surfactants to enhance foam stability. Experimental results showed that N2 foams were more stable than CO2 foams. It was observed that foam half-life decreased with the increase in temperature. Among all the surfactants, AOS foams showed the most promising thermal stability at high temperatures. Moreover, with the addition of stabilizing agents, foam's half-life was enhanced. Stabilizing agents such as crosslinker and GO dispersion showed the most stable foams with half-life recorded at 20 min and 17 min, respectively, at 200°C and 1000 psi. Finally, pressure also showed a positive effect on foam stability; with increased pressure, foam half-life was increased. Based on the experimental data, analytical models for the effect of temperature and pressure were developed, considering foam degradation is a first-order kinetic reaction that linearly depends on the foam drainage mechanism. The effect of temperature on foam half-life was studied as an exponential decay model. In this model, foam half-life is a function of drainage rate constant (DA) and activation energy (Ea) of the foam system. The effect of pressure on foam half-life was found to obey a power-law model where an increase in pressure showed an increase in foam half-life. Furthermore, a linear relation was studied for the effect of pressure on foam activation energy and drainage rate. Then the, combined effects of temperature and pressure were studied, which yielded an analytical model to predict the foam stabilities in terms of half-life for different foam compositions. This research indicates that with an appropriate selection of surfactants and stabilizing agents, it is possible to obtain stable foams, which could replace conventional water fracturing fluid under EGS conditions. / Mechanical Engineering

<p>Silicones are a class of polymeric materials broadly used in numerous commercial applications, primarily due to the significant advantages they poses over their carbon-based analogues. The technology utilized to synthesize them is rather mature, and most ‘new’ synthetic strategies involve only incremental changes to the existing norm. The high level of structural control that has become the hallmark of organic synthesis and increasingly of polymer chemistry is essentially absent from silicone chemistry. The origin of this deficiency is the susceptibility of silicone polymers to redistribution (metathesis/rearrangement) under acidic and basic conditions, which will destroy any existing controlled architectures. The Piers-Rubinsztajn reaction, catalyzed by tris(pentafluorophenyl)borane (B(C₆F₅)₃), involves the direct coupling between an alkoxysilane and hydrosilane forming a new siloxane linkage, (R₃Si-OMe + H- SiR’₃ → R₃Si-O-SiR’₃ + Me-H). The reaction avoids any unwanted acidic/basic reaction conditions and has been shown previously to provide an efficient route to precise, well-defined silicones.</p> <p>Herein, the functional tolerance of the Piers-Rubinsztajn reaction is reported. It has been shown that in the presence of Lewis basic functional groups (such as – OH, -NH₂, -SH) unwanted side reactions result. However in the presence of haloalkanes and alkenes the reaction is fully tolerant, leading to the synthesis of over twenty new, well-defined functional silicones.</p> <p>The ability to utilize prepared functional silicones in common organic transformations is also reported. It has been shown that prepared halocarbon- modified silicones can readily be converted to their subsequent azido derivatives and tethered to alkyne-modified poly(oxyethyene) (PEG or PEO) of a variety of molecular weights. This led to the synthesis of over fifteen new, well-defined silicone surfactants. Structure activity relationships have also been reported for the synthesized surfactants, showing that subtle manipulations to the silicone hydrophobe can substantially alter the properties the surfactants possess. The use of thiol-ene click chemistry which involves the reaction between prepared well-defined alkene containing silicones and thiol modified poly(oxyethylene) of varying molecular weights is also reported, providing another route to well- defined silicone based surfactants.</p> <p>The use of the Piers-Rubinsztajn reaction in the synthesis of larger, well-defined silicone based macrostructures is also reported. It has been shown that through alternation between the Piers-Rubinsztajn reaction and platinum catalyzed hydrosilylation, well defined silicone dendrimers can be obtained with relative ease through a combination of both divergent and convergent growth methods.</p> <p>Finally, a new method for the preparation of both silicone elastomers and silicone foams is reported. Through use of the Piers-Rubinsztajn reaction, elastomers can be readily obtained. A detailed analysis of the many factors that may alter the overall properties of the elastomers produced including solvent volume, crosslinker concentration and type and the molecular weight of the starting hydride terminated polydimethylsiloxane (H-PDMS-H) is discussed.</p> <p>Taking advantage of the volatile hydrocarbon byproducts of the Piers-Rubinsztajn reaction, silicone foams can also be prepared using this method. A study analogous to that carried out on the silicone elastomers is also reported, showing that through subtle manipulations to the silicone foam formulations, significant changes to the materials properties can be obtained.</p> / Doctor of Science (PhD)

Exponential growth of heat flux densities in commercial and industrial electronics, and compact heat exchangers demand surfaces and heat sinks with high dissipation rate capabilities. Among different technologies proposed to meet these demands, high-porosity metal foams have attracted the attention of many investigators due to their higher surface area densities as well as higher thermal performance due to the turbulence and tortuosity generated in the flow due to their structure. One of the disadvantages of such metal foams, however, is the attendant higher pressure drop or pumping power penalty. This thesis was undertaken to investigate whether channels partially filled with metal foams can reduce the required pumping power with a minimal loss in thermal performance. The thermo-hydraulic (T-H) performance factor J/F<sup>1/3, where J is the Colburn-J factor and F is the friction factor, was used to compare the relative performance of foams for various values of blocking fractions (B), where B is defined as the ratio of the height of the foam to the height of the channel. The metal foam samples considered were 10 PPI (pores per inch) 6101-T6 Aluminum, with porosity of ∼ 94 − 96%, and B of 1/6, 1/3, 2/3, 5/6, and 1. Each of these samples was attached to an aluminum slab embedded in one of the walls, which had a patch heater that acted as a heat source. A modification was made to all B < 1 configurations by attaching an aluminum plate on top, which then separated the foam-free and the foam-filled flows completely. These configurations are denoted by a 'P' in their names (e.g. B = 1/3P is the plated modification of B = 1/3). Experiments were conducted in an in-house designed wind tunnel, with a test section of 45" in length and a cross-section of 3"X3". Reynolds number (based on channel hydraulic diameter and inlet velocity) was varied from 1,000 to 15,000 to capture the flow domains from laminar to turbulent. The data obtained for the three scenarios namely - 1. Controlled-Flow Scenario 2. Pumping Power Variation with Temperature Difference, and 3. Fan-Based System were analyzed for their thermo-hydraulic performance. The extreme low blocking fractions are evaluated and compared against the dimpled/protruded surfaces, and were found to give superior performance, hence displaying potential as good turbulators. The plated configurations were found to perform better in almost all scenarios when compared to their non-plated counterparts. Furthermore, a new simplified analytical model is introduced that considers the flow in the partially-blocked region as two separate 'parallel' flows, one in the foam-free region and the other in the foam-filled region. The comparison between this novel approach and the analytical solution from the literature shows good agreement, suggesting that this simplified model may be appropriate. This model is then used for determining the foam-filled region flow ratios for the performed experiments, and a correlation is presented. / Master of Science / Portable devices, such as laptops, and mobile phones are trending towards miniaturization and simultaneously becoming more power-hungry, leading to ever-increasing heat flux densities. Growing energy and technology demands require high thermal dissipation rates to be achieved in equipment such as industrial and commercial electronics, data centers, heat exchangers in automobiles, and power plants - both renewable and non-renewable. One of the best ways to enhance convective heat transfer is by increasing the heat transfer surface area. This is traditionally done using fins. A much higher surface area can be achieved using a metal foam instead, along with improving the turbulent mixing of the fluid. The flow through the metal foam, however, faces a higher pressure drop penalty which is one of the major reasons for a continued preference for fins. In this experimental study, we aim at minimizing this pressure drop penalty of a metal-foam heat-sink along with maintaining a respectable heat transfer performance through 'partial-blocking' (filling) of the channel, where the height of the foam is lower than the total channel height. The ratio of metal foam height to the channel height is named as blocking fraction B. A general comparison of the hydraulic, thermal, and thermo-hydraulic (T-H) performance reveals that the ∼ 83.3% plated configuration is capable of superseding the baseline of full blockage. The 'plating' here denotes a slight modification - a solid plate rests on top of the metal foam, separating the foam-free and foam-filled flow. For applications with Re > 10000, ∼ 33.3% plated configuration is highly recommended. For fan-based systems, ∼ 83.3% plated, ∼ 33.3% plated, and 33.3% non-plated configurations emerge as possible alternatives to the fully-blocked case. Furthermore, while considering partial configurations, it is shown that one should go for lower PPI metal foams to improve the flow ratio inside the metal foam. For pressure-drop critical equipment, ∼ 16.7% configuration is found to perform better than the conventional double-protruded walls and other turbulence-enhancing surface treatments. Finally, this thesis presents a novel and simplified approach for estimating the flow ratios for partially-blocked channels using scaling analysis.

Thermal energy storage (TES) systems based on renewable energy sources (concentrated solar, wind, and photovoltaic etc.) are crucial to reducing dependence on conventional energy generation systems and reducing renewable energy’s intermittent nature. TES can be utilized in conjunction with concentrated solar power (CSP) in particle-based power cycles where the particles can be charged (heat addition) using solar energy and then discharged (heat extraction) using particle-based heat exchangers (HX). Efficient particle based HXs are vital in coupling heat transfer fluid (HTF) from thermal receivers to power cycle working fluid (WF). Heat transfer enhancement is essential for adopting particle-based moving packed-bed heat exchangers (MPBHXs) in next-generation TES systems, as MPBHXs usually exhibit low particle bed-to-wall heat transfer coefficients and total heat transfer rate. This dissertation focuses on addressing the limitations of MPBHXs by computationally studying the heat transfer performance enhancement due to granular flows in metal foam-based MPBHXs and reactive flow-based MPBHXs. Comprehensive multidimensional, multiscale, and multiphysics models are developed to predict the TES/TCES (Thermochemical energy storage) performance accurately. First, the flow properties through metal foams are determined, followed by granular flow through metal foam-based particle-to-sCO2 HXs to predict the heat transfer enhancement. Then, granular flows with reactive and sensible heat-only particles are studied in particle-to-sCO2 HXs to predict the heat transfer enhancement, followed by the development of discrete element models (DEM) in inclined moving bed granular flows to study particle-scale heat and mass transfer. Overall, this study provides valuable insights into effective modeling of granular flows from continuum to discrete scales and improved design and operation of particle-based heat exchangers and thermochemical reactors.