Dans cette thèse nous avons simulé la distribution d’éléments traces en Méditerranée, dans le but de mieux contraindre la circulation thermohaline et les cycles biogéochimiques. Pour cela, nous avons utilisé le modèle dynamique à haute résolution NEMO-MED12 couplé avec le modèle de biogéochimie marine PISCES.La Méditerranée offre un cadre particulièrement attrayant pour l’étude des traceurs géochimiques. Il s’agit d’une mer semi-fermée, ce qui permet de mieux contraindre les différentes sources et puits des éléments (poussières atmosphériques, fleuves …). Plus particulièrement, nous avons modélisé le tritium (3H), traceur transitoire couramment utilisé pour l’étude de la variabilité interannuelle de la circulation thermohaline. Nous avons aussi simulé les isotopes de l’hélium (3He, 4He), traceurs conservatifs injectés par l’activité volcanique sous-marine et les sédiments, pour contraindre la circulation profonde. Nous nous sommes intéressés également à la composition isotopique du Néodyme (Nd), traceur permettant d’étudier les échanges de matière avec les marges continentales, ainsi qu’à la modélisation du radiocarbone (14C), qui permet d’avoir des informations uniques sur les variations de la circulation thermohaline et des processus de mélange sur les périodes récentes et passées.Cette ensemble de simulations nouvelles et la confrontation avec des observations récentes d’éléments traces issues de différents programmes d’observation (GEOTRACES, METEOR, PALEOMEX), a apporté une expertise nouvelle et supplémentaire sur la dynamique et les cycles biogéochimique en mer Méditerranée. Ce travail contribue à améliorer le modèle régional NEMO/Med12/PISCES développé pour ce bassin, apporte une expertise essentielle pour développer notre aptitude à prévoir l’évolution future de ce bassin sous la pression du changement anthropique. / Useful diagnostics of the ventilation of the ocean’s interior are derived from geochemical tracers characterized by simple boundary conditions at the ocean’s surface, and a conservative behavior in marine waters. In this thesis, we simulated explicitly some trace elements distribution in the Mediterranean to better constrain the thermohaline circulation and biogeochemical cycles. We used a high resolution physical/biogeochemical model NEMO-MED12-PISCES.The Mediterranean offers a particularly attractive setting for studying geochemical tracers. It’s a semi-enclosed basin, which makes it easier to quantify the various sources and sinks of the elements (atmospheric dust, rivers ...). In particular, we modeled tritium (3H), a transient tracer currently used for the study of the interannual variability of the thermohaline circulation. We also simulated helium isotopes (3He, 4He), useful tracers for investigating the deep ocean circulation.We have simulated the isotopic composition of neodymium (Nd), tracer adapted to investigate the exchanges between dissolved/particulate phases, with the continental margins, and to constrain the modern and paleo thermohaline circulation, as well as radiocarbon (14C), an ideal tracer for studying air-sea gas exchange and for assessing the ventilation rate of the deep water masses over very long timescales.This study is part of the work carried out to assess the robustness of the NEMO-MED12 model, which will be used to study the evolution of the climate and its effect on the biogeochemical cycles in the Mediterranean Sea, and to improve our ability to predict the future evolution of the Mediterranean Sea under the increasing anthropogenic pressure.

科学研究費補助金 研究種目:基盤研究(C)(2) 課題番号:07650870 研究代表者:藤澤 敏治 研究期間:1995-1996年度

科学研究費補助金 研究種目:基盤研究(C)(2) 課題番号:09650806 研究代表者:藤澤 敏治 研究期間:1997-1998年度

Cette thèse concerne la réalisation des films minces d’oxydes et l’étude de leurs propriétés physiques pour les cellules photovoltaïques (PV) et les modules thermoélectriques. Dans une première partie, les propriétés de l’oxyde de titane TiOx (1,45<x<2) sont mises en évidence pour une utilisation en tant qu’oxyde transparent conducteur optiquement actif à disposer en face avant des cellules PV ou, comme couche de couplage optique à intercaler entre le métal réflecteur et la couche absorbante d’une cellule PV. Les couches sont déposées par ablation laser pulse (PLD). Cette méthode permet d’obtenir des couches stoechiométriques ou déficitaires en oxygène grâce au contrôle de la pression d’oxygène pendant le dépôt. Les couches sont dopées par Nb pour un gain en conductivité électrique et/ou par Nd pour la conversion des photons UV en photons du Proche IR. Les films d’une part, isolants, transparents et luminescents ou d’autre part, conducteurs et absorbants ont été obtenus. La présence de polarons et/ou de bipolarons dans les couches TiO₁,₄₅₋₁,₆₀ explique la discontinuité observée sur leurs courbes de thermoconductivité. Une seconde partie du manuscrit concerne la thermoelectricité ou il est question de modifier les propriétés des cobaltites de calcium pour la conversion en énergie électrique des gradients de température faibles, centres autour de 300-365 K. Le contrôle de la concentration en oxygène des films a permis d’obtenir les phases polymorphes CaxCoO₂, Ca₃Co₄O₉, et Ca₃Co₄O₆,₄₋₆,₈ présentant des comportements semiconducteurs ou métalliques en fonction de la température de dépôt. Les films Ca₃Co₄O₆,₄₋₆,₈ montrent de faibles résistivités (3,8-6 mΩ.cm) et des coefficients de Seebeck élevés (S) ≥ 1000 μV/K qui doivent être confirmes pour que de tels films soient utilisés dans les thermogénérateurs. / This thesis concerns the realization of oxide thin films and the study of their properties for photovoltaic or thermoelectric devices. In the first part, the TiOx properties are studied for use as an optically active transparent conductive oxide to put in front of the PV cells or, as optical coupling layer to interpose between the metal reflector and the absorbent layer of a PV cell. The layers are deposited by pulsed laser deposition (PLD). This method allows to get stoichiometric or oxygen deficient layers by controlling the oxygen partial pressure during the growth. The layers are doped with Nb to enhance electrical conductivity and/or with Nd for the conversion of Ultra-Violet photons to Near Infra-Red photons. Insulating and transparent layers, luminescent layers or conducting and absorbent layers are obtained. The TiO₁,₄₅₋₁,₆₀ films show polaronic or bipolaronic conductivity and exhibited the jump of electrical conductivity with jump height and temperature depending on the nature of the dopants. A second part of the manuscript concerns thermoelectricity in which the properties of cobalt calcium oxide are modulated for an efficient conversion of low temperature gradients centered at 300-365K. The control of the oxygen concentration of films allows to obtain the polymorphic phases CaxCoO₂,Ca₃Co₄O₉ and Ca₃Co₄O₆,₄₋₆,₈ having metallic or semiconducting behavior depending on the deposition temperature. The Ca₃Co₄O₆,₄₋₆,₈ films show high Seebeck coefficients (S) ≥ 1 000 μV/K and low electrical resistivity (3.8 to 6 mΩ.cm). Such interesting values have to be confirmed by additional experiments in order to be used as thermoelectric films.

V dnešní době je kladen vysoký nárok na účinnost elektrických zařízení a to jak ze strany provozovatele, tak i legislativy. Nejlepší účinnosti dosahují synchronní motory s permanentními magnety umístěnými na povrchu rotoru (SMPM), se kterými lze i u malých motorů dosáhnout účinnosti nad 90%. Nicméně tyto motory jsou z důvodů použití magnetů ze vzácných zemin, např. NdFeB, drahé a jsou schopny provozu pouze s frekvenčním měničem. Z cenových důvodů jsou hledány levnější alternativy k SMPM motorům. Jedním z typů motorů, kterým lze SMPM nahradit je synchronní reluktanční motor s permanentními magnety (PMASR). Tento motor je cenově výhodnější, protože používá menší množství magnetů, při zachování podobných, mnohdy i lepších vlastností, nicméně neodpadá potřeba použití frekvenčního měniče. Navíc je zde možnost použití levnějších feritových magnetů a tím ještě výrazněji snížit cenu motoru. V této práci bude PMASR topologie popsána důkladněji včetně elektromagnetického návrhu metodou konečných prvků. Bude provedena i mechanická analýza zvoleného optimálního modelu. Výsledky dosažené metodou konečných prvků budou následně porovnány s analytickým modelem. Z navrženého modelu bude vyroben prototyp a naměřené výsledky budou porovnány s výpočty.

Magnesium alloys are being developed as advanced materials for structural applications where reduced weight is a primary motivator. Alloying can enhance the properties of magnesium without significantly affecting its density. Essential to alloy development, inclusive of processing parameters, is knowledge of thermodynamic, kinetic, and mechanical behavior of the alloy and its constituents. Appreciable progress has been made through conventional development processes, but to accelerate development of suitable wrought Mg alloys, an integrated Materials Genomic approach must be taken where thermodynamics and diffusion kinetic parameters form the basis of alloy design, process development, and properties-driven applications. The objective of this research effort is twofold: first, to codify the relationship between diffusion behavior, crystal structure, and mechanical properties; second, to provide fundamental data for the purpose of wrought Mg alloy development. Together, the principal deliverable of this work is an advanced understanding of Mg systems. To that end, the objective is accomplished through an aggregate of studies. The solid-to-solid diffusion bonding technique is used to fabricate combinatorial samples of Mg-Al-Zn ternary and Mg-Al, Mg-Zn, Mg-Y, Mg-Gd, and Mg-Nd binary systems. The combinatorial samples are subjected to structural and compositional characterization via Scanning Electron Microscopy with X-ray Energy Dispersive Spectroscopy, Electron Probe Microanalysis, and analytical Transmission Electron Microscopy. Interdiffusion in binary Mg systems is determined by Sauer-Freise and Boltzmann-Matano methods. Kirkaldy*s extension of the Boltzmann-Matano method, on the basis of Onsager*s formalism, is employed to quantify the main- and cross-interdiffusion coefficients in ternary Mg solid solutions. Impurity diffusion coefficients are determined by way of the Hall method. The intermetallic compounds and solid solutions formed during diffusion bonding of the combinatorial samples are subjected to nanoindentation tests, and the nominal and compositionally dependent mechanical properties are extracted by the Oliver-Pharr method. In addition to bolstering the scantly available experimental data and first-principles computations, this work delivers several original contributions to the state of Mg alloy knowledge. The influence of Zn concentration on Al impurity diffusion in binary Mg(Zn) solid solution is quantified to impact both the pre-exponential factor and activation energy. The main- and cross-interdiffusion coefficients in the ternary Mg solid solution of Mg-Al-Zn are reported wherein the interdiffusion of Zn is shown to strongly influence the interdiffusion of Mg and Al. A critical examination of rare earth element additions to Mg is reported, and a new phase in thermodynamic equilibrium with Mg-solid solution is identified in the Mg-Gd binary system. It is also demonstrated that Mg atoms move faster than Y atoms. For the first time the mechanical properties of intermetallic compounds in several binary Mg systems are quantified in terms of hardness and elastic modulus, and the influence of solute concentration on solid solution strengthening in binary Mg alloys is reported. The most significant and efficient solid solution strengthening is achieved by alloying Mg with Gd. The Mg-Nd and Mg-Gd intermetallic compounds exhibited better room temperature creep resistance than intermetallic compounds of Mg-Al. The correlation between the concentration dependence of mechanical properties and atomic diffusion is deliberated in terms of electronic nature of the atomic structure.

<p dir="ltr"><a href="" target="_blank">The electrification of the transportation sector is pivotal in reducing greenhouse gas emissions and decreasing dependence on fossil fuels. Central to this transition are battery electric vehicles (BEVs) and other clean energy technologies, which rely heavily on critical materials (CMs) such as cobalt, lithium, neodymium, and nickel. </a>These materials are essential for the performance of batteries, advanced electronics, and other components in BEVs. <a href="" target="_blank">However, the limited availability of these CMs poses potential constraints on the widespread adoption of such technologies.</a></p><p dir="ltr">This research delves into the implications of widespread BEV adoption on the demand for CMs in the United States, with a focus on both light-duty vehicles (LDVs) and medium- and heavy-duty vehicles (MHDVs). Various market penetration scenarios were analyzed, revealing that while MHDVs require more CMs per vehicle, the sheer volume of LDV sales drives the overall CM demand, particularly in a scenario with 100% BEV adoption. Key findings highlight that cobalt, graphite, lithium, neodymium, and nickel are critical for BEVs, whereas palladium and rhodium are more crucial for internal combustion engine vehicles (ICEVs). Also explored is the impact of lightweighting on LDVs, revealing that while substituting steel with aluminum increases the total CM quantity per vehicle, it reduces the vehicle's mass, operational energy consumption, and the demand for high-concern battery-related CMs. Additionally, changing the battery cathode chemistry from NMC622 to LFP significantly reduces CM use but increases the demand for strategic materials like copper and phosphorus due to the lower energy density of LFP-based batteries.</p><p dir="ltr">The research also highlights the importance of rare earth permanent magnets (REPMs), <a href="" target="_blank">particularly Neodymium-Iron-Boron (NdFeB) magnets, in clean energy technologies such as electric vehicles and wind turbines.</a> Neodymium, a critical material, faces supply chain risks. To lessen these risks, circular economy strategies have been proposed, including the recovery of needed materials from end-of-life (EoL) products. <a href="" target="_blank">A dynamic material flow analysis (MFA) model was developed to forecast such EoL flows for products containing REPMs and assess the recoverable neodymium from these EoL products. </a>The results indicate that even a modest recycling efficiency of 15% could meet 12% of the Nd demand for EVs by 2050, with reuse meeting up to 70% of the demand.</p><p dir="ltr">With the dynamic MFA model showing that circular economy principles could meet up to 70% of future neodymium demand in 2050, the next step was to investigate the techno-economic feasibility of recycling REPMs. A techno-economic assessment model was developed for establishing a magnet-to-magnet recycling facility for REPMs. Results revealed a net present value (NPV) of $8,867,111 over 20 years, a payback period of 3 years, and an internal rate of return (IRR) of 53%, providing a compelling case for investment in recycling infrastructure. Sensitivity analyses point to the selling price of recycled magnets, feedstock purchase price, facility throughput, and labor costs as the most influential factors on profitability.</p><p dir="ltr"><a href="" target="_blank">Additionally, this research explored the challenges and opportunities in the disassembly and recycling of EoL EV components, particularly traction motors containing REPMs. The complexity of disassembly, driven by varying component sizes and designs, is identified as a significant barrier. By evaluating manual disassembly times and proposing potential automation solutions, the study aims to streamline the disassembly process, thus facilitating more efficient recycling and remanufacturing operations.</a></p><p dir="ltr">The key contributions of this research are summarized as follows:</p><p dir="ltr">· Evaluated the vehicle CM demand of ICEVs and BEVs for LDVs and MHDVs and explored the impact of lightweighting and changing the battery cathode chemistry from NMC622 to LFP on CM demands.</p><p dir="ltr">· Developed a dynamic material flow analysis (MFA) model to forecast end-of-life (EoL) flows of products containing REPMs and assess the recoverable neodymium from these EoL products.</p><p dir="ltr">· Developed a techno-economic assessment (TEA) model to evaluate the viability of a magnet-to-magnet recycling facility.</p><p dir="ltr">· Performed disassembly analysis to assess the ease with which EoL BEV transmissions can be disassembled with a specific focus on the retrieval of traction motors (which house the REPMs) for potential reuse or remanufacturing.</p>

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.