Dans l'objectif de combler le gap entre l'offre et la demande en propène, la réaction d'oxydation déshydrogénante du propane (ODHP) est une solution alternative à la réaction de déshydrogénation directe. Les hydroxyapatites (HAp) modifiées au vanadium sont des matériaux bi-fonctionnels aux propriétés acido-basiques et redox intéressants pour cette réaction. L'objectif de cette thèse est d'étudier le comportement catalytique de ces systèmes et d'établir des relations entre structure et réactivité. Par le contrôle des conditions de synthèse et pourvu que le pH soit maintenu élevé (~9), la solution solide Ca10(PO4)6-x(VO4)x(OH)2 est obtenue dans toute la gamme de composition (x 0→ 6), alors que pour un pH inférieur, un mélange de phases d'HAps au vanadium et de Ca2V2O7 est obtenu pour x ≥ 4. Pour la solution solide, contrairement à la sélectivité en propène, la conversion en propane n'augmente pas avec la teneur en vanadium non exposé en surface. L'activation de la liaison C-H du propane s'explique par une propriété intrinsèque à la structure HAp, en lien avec la formation thermiquement activée d'anions O2- très basiques. Leur formation in situ résulte de la déshydratation progressive des colonnes d'ions OH- via le processus de conduction ionique par les protons, exalté sous conditions réactionnelles. L'organisation du vanadium sous la forme de tétramères dans Ca2V2O7 au lieu de tétraèdres isolés dans la seule solution solide favorise les échanges redox et explique l'augmentation de la sélectivité. Le contact intime entre les deux phases et la formation d'une interface cohérente permet un optimum de rendement en propène du fait de la synergie des propriétés des deux phases. / In order to fill the gap between propene supply and demand, the oxidative dehydrogenation of propane (ODHP) is an alternative solution to the direct dehydrogenation process. Vanadium-modified hydroxyapatites (HAp) are bifunctional catalysts combining acid-base and redox properties which were shown to be of interest for the ODHP reaction. In order to optimize this system, the aim of the work was to investigate the catalytic behavior of the vanadium-modified hydroxyapatites and to establish structure reactivity relationships. By peculiar attention was devoted to the control of synthesis. Provided high pH value is maintained during the synthesis, the Ca10(PO4)6-x(VO4)x(OH)2 solid solution was successfully obtained for x 0→ 6, whereas at lower pH, a mixture of Vx-HAp solid solution and of Ca2V2O7 was obtained from x ≥ 4. For the solid solution, contrary to propene selectivity, the propane conversion does not depend on the vanadium content, unexposed on the surface. The activation of the C-H bond of propane is controlled by an intrinsic properties of the HAp structure, in relation with the thermally activated formation of strong basic O2- anions. Their in situ formation results from the progressive dehydration of OH- columns via an ionic conduction process by protons that is enhanced under catalytic conditions. Due to the tetrameric environment of vanadium in Ca2V2O7 against isolated tetrahedra in the solid solution, redox exchanges are facilitated, improving the selectivity in propene. The intimate contact between the two phases and the formation of a coherent interface leads to an optimal yield in propene, due to synergistic effects of the two phases.

Les aciers avancés à haute résistance (AHSS) de 3ème génération ont l’avantage de combiner résistance et ductilité. Ces aciers multi-phasés sont appréciés pour les applications dans l’industrie automobile pour leurs propriétés mécaniques, dues notamment à la présence d’austénite métastable permettant une transformation induite par la plasticité (effet TRIP- Transformation Induced Plasticity).L’objectif de ce travail a été d’étudier l’effet du microalliage sur les transformations de phases et la précipitation dans de tels aciers. Trois nuances ont été étudiées : une référence sans microalliage, une avec ajout de niobium et une avec ajout de vanadium. Elles ont été caractérisées au fil de la route métallurgique composée d’un recuit intermédiaire et d’un recuit final caractéristique des aciers bainitiques à effet TRIP.Des méthodes ex-situ et in-situ ont été mises en oeuvre. Les caractérisations in-situ pendant les traitements thermiques incluent une étude des transformations de phases par diffraction de rayons X à haute énergie (HEXRD) et une étude de la précipitation par diffusion de rayons X à petits angles (SAXS), utilisant le rayonnement synchrotron.La morphologie des grains a été observée par microscopie optique et diffraction d'électrons rétrodiffusés (EBSD) au Microscope Electronique à Balayage (MEB). L’imagerie des précipités a été effectuée par Microscopie Electronique en Transmission (MET) en imagerie en champ sombre, leur composition a été précisée par analyse dispersive en énergie (EDS) et leur localisation étudiée grâce à l’outil de nano-diffraction ACOM/ASTAR.L’ensemble de ces expériences a permis de mettre en évidence l’effet du traitement thermique et de la composition chimique sur la quantité d’austénite présente ainsi que sur sa teneur en carbone, qui sont les principaux paramètres contrôlant l’effet TRIP. La présence du microalliage se traduit par des variations de ces paramètres, liés à la fois à la présence de précipités contenant ces éléments et à leur présence en solution solide. / 3rd generation Advanced High Strength Steels (AHSS) have the advantage of combining strength and ductility. These multi-phase steels are appreciated for applications in the automotive industry for their mechanical properties, notably due to the presence of metastable austenite allowing Tranformation Induced Plasticity (TRIP effect).The objective of this work was to study the effect of microalloying on phase transformations and precipitation in such steels. Three grades have been studied: a reference without microalloying, one with niobium addition, and one with vanadium addition. They have been characterised through the metallurgical route composed of an intermediate annealing, following by a final annealing characteristic of TRIP-assisted bainitic steels.Both ex-situ and in-situ methods have been applied. In-situ characterisation during thermal treatments includes phase transformation study by High-Energy X-ray Diffraction (HEXRD) and precipitation study by Small Angle X-ray Scattering (SAXS), both performed with synchrotron radiation.Grain morphology has been observed by optical microscopy and Electron Back-Scatter Diffraction (EBSD) in a Scanning Electron Microscope (SEM). Imaging of precipitates has been made in Transmission Electron Microscopy (TEM) via dark-field imaging, their composition has been evauated by Energy Dispersive Spectroscopy (EDS) and their localization studied thanks to the nano-diffraction tool ACOM/ASTAR.All these experiments made it possible to highlight the effect of heat treatment and chemical composition on the amount of austenite present and on its carbon content, which are the main parameters controlling the TRIP effect. The presence of the microalloying results in variations in these parameters, related both to the presence of precipitates containing these elements and to their presence in solid solution.

Mesoporous thin films are promising architectures for positive electrodes in Li-ion battery applications. A particular challenge in this field has been successful templating of vanadium-based oxides, materials known for their ability to host lithium, since their thermal instability and complex vanadium chemistry hinder templating through traditional soft-chemistry approaches. To address these technical problems we here develop the soft-templating of vanadium and niobium mixed oxides based on Evaporation Induced Micelles Packing using thermally stable polystyrene-b-polyethyleneoxide structuring agents. In-situ thermal monitoring via ellipsometry allows successful navigation of the thermal stability landscape. TEM and AFM analyses reveal homogeneous wormlike mesoporous structures whose pore and inorganic wall sizes can be tuned from 15 to 100 nm by changing the hydrophobic/hydrophilic surfactant chain lengths. Ellipsometric porosimetry shows that 100 nm thick films with a 15 nm pore size displays 30% electrolyte accessible porosity. The interconnected tridimensional mesoporous network has been highlighted by electronic tomography. Thicker films up to 1.3 µm are prepared by a multidipping process. The superiority of such nanoarchitectures compared to non porous materials in terms of electrochemical properties such as capacity are revealed using cyclic voltammetry.

Elektroden aus Legierungen der Übergangsmetalle Vanadium, Titan und Niob und der reinen Metalle reagieren in Abhängigkeit von der Zusammensetzung und des mit ihnen im Kontakt stehenden wässrigen Elektrolyten in höchst unterschiedlicher Weise. Für eine systematische Untersuchung der elektrochemischen Eigenschaften der Elektroden wurden neben den reinen Metallen binäre und ternäre Legierungen aus Vanadium, Titan und Niob, die jeweils Vanadium enthalten, hergestellt. Es wurden zum ersten Mal zusammenhängend ihre physikalischen und chemischen Eigenschaften durch Strukturuntersuchungen und Untersuchungen der Zusammensetzung der Oberfläche sowie der Morphologie bestimmt. Von den, sich mit einer halbleitenden Oxidschicht überziehenden Metallen, wurden die Halbleitereigenschaften im Elektrolytkontakt studiert, die grundlegenden Korrosionseigenschaften sowie ihr elektrochemisches Verhalten als Elektrodenmaterial in potentiometrischen Zellen und durch Strom-Spannungsmessungen bestimmt. Zur Aufklärung der Kinetik der Oxidschichtbildung wurden potentiostatische Stromtransienten ermittelt und mit bekannten Modellen verglichen.

Darbo tikslas yra ištirti etaloninių vanadžio pentoksido ir dioksido Rentgeno fotoelektronų spektrus siekiant nustatyti cheminį poslinkį tarp oksidų V 2p spektrų smailių. Darbe išsamiai aprašytos vanadžio dioksido ir prntoksido struktūros, oksidų savybės, Rentgeno fotoelektronų spektroskopijos metodo pagrindai bei V2O5 ir VO2 Rentgeno fotoelektronų spektrų ypatumai. Aprašyti atliktų eksperimentų metodai. Pateikti eksperimentų ir literatūrinės duomenų bazės analizės rezultatai. Atliktas darbas leido nustatyti sekančius faktus: cheminis poslinkis tarp vanadžio dioksido ir pentoksido etaloninių bandinių Rentgeno fotoelektronų spektrų V 2p3/2 smailių lygus 0.7 eV matuojant spektrus spektrometru XSAM 800 (Kratos Analytical, Anglija); literatūrinių duomenų analizę parodė, kad tikimiausia cheminio poslinkio vertė tarp V 2p3/2 smailių įvairiuose vanadžio junginiuose lygi 1.1 eV; skirtumas tarp eksperimentiškai gautos cheminio poslinkio vertės ir analogiško dydžio gauto iš literatūrinių duomenų analizės sąlygotas tuo, kad buvo matuojami gryni VO2 ir V2O5 bandiniai, o analizei buvo naudojama duomenų visumą apie įvairius vanadžio junginius. / The main aim of the presented work was to investigate the chemical shift between XPS V 2p peaks of standard V2O5 and VO2 samples. The structure and physical properties of vanadium dioxide and pentoxide, X-ray photoelectron spectroscopy basis and some singularities of these oxides XPS spectra are presented. The experimental methods, the results of experiments and the literature analysis results are described. The executed work has allowed establishing following facts: the chemical shift between vanadium dioxide and pentoxide standard samples XPS V 2p peaks is equal to 0.7 eV; the analysis of the literature base shows that this shift for various vanadium compounds is 1.1 eV; the difference between measured chemical shift and chemical shift value established from literature analysis is caused because XPS spectra of pure oxides samples was measured in present work and the analysis of the literature base was performed for various vanadium compounds.

In an effort to reduce global emissions by electrifying vehicles and machines with internal combustion engines has led to the development of batteries that are more powerful and efficient than the common lead acid battery.  One of the most popular batteries being used for such an installation is lithium ion, but due to its short effective usable lifetime, charging time, and costs has driven researcher to other technologies to replace it.  Vanadium redox flow batteries have come into the spotlight recently as a means of replacing rechargeable batteries in electric vehicles and has previously be used mainly to store energy for load leveling.  It possesses many qualities that would be beneficial to electrify vehicles.  The battery has the ability for power and energy to be sized independently which is not dissimilar to internal combustion vehicles.  It also has the potential for a tolerance to low discharges, fast response time, and can quickly be refueled by replacing the electrolyte; just like is done when a car refuels at the gas station.  The purpose of the study is to determine the possibility of using vanadium redox flow batteries to power heavy construction equipment, a wheel loader, with a finite amount of space available for implementation.  A model has been designed in MATLAB to determine how long the battery could last under typically applications for the wheel loader which needs a peak power of 200 kW.  From the volume available it has been determined that the battery can be installed with an energy capacity of 148 kWh.  The results of the model show that vanadium redox flow batteries can be used to power a wheel loader but due to the limiting energy density and cell components it remains to be impractical.

As society strives to transition for sustainable energy generation is it a major challenge to optimize and develop the renewable energy generation that currently exists, both in terms of individual components and their interactions in the entire energy system. The generation from renewable sources is often irregular and not always when the demand arises. By being able to store the excess energy generated and then deliver it when the demand occur results in a more sustainable energy system. Flow batteries are a possible technology for energy storage. An important component of flow batteries are vanadium and to find methods for extracting vanadium in an economical way is an important step in the development of this technology. The idea behind the thesis was therefore to investigate different extraction methods for vanadium where the most promising methods, from an economic and energy perspective, are examined in more detail. The vanadium should then be used to electrolyte in flow batteries. It has also been examined how the cost is affected by moving a planned facility for extraction from the ashes to a developing country with lower personnel costs. In the thesis was also included to explore similar projects on a larger scale conducted in Sweden, how the view of vanadium is from an EU perspective and how flow batteries can be a part of an energy system. The methods considered most promising is extraction from mineral mining and extraction from ashes. A planned production plant has been dimensioned for both processes of production and energy demand is calculated. The study showed that both processes are expected to produce vanadium below current purchase price, which would then contribute to a cheaper production cost of flow batteries. It turned out that the production of vanadium from ash extraction would be significantly reduced by moving the business to a developing country. The operation stage in the mining operation which accounts for the highest energy demand is the size reduction of the ore. In the extraction process of vanadium from ash, it is primarily the fusion furnace and the fly ash filter required which has the highest energy demand. The similar extraction projects investigated was, from ashes, the so-called SOTEX process in Stenungsund and the mineral mining process had the Ranstad project as reference. The EU approach to vanadium is currently that the metal is not classified as a critical raw material but if economic instability would occur in any of the major manufacturing countries it would be considered as a more critical raw material. Flow batteries functioning as energy storage in a PV hybrid system was investigated and it was concluded that flow batteries are technically well suited for energy storage in this type of system. / Då samhället strävar efter att övergå till en hållbar energiproduktion är det en stor utmaning att effektivisera och utveckla den förnyelsebara energiproduktion som idag finns, både när det gäller enskilda komponenter och deras samspel i hela energisystem. Produktion från förnyelsebara energikällor sker ofta ojämnt och inte alltid när behovet uppstår. Genom att kunna lagra den överskottsenergi som produceras och sedan leverera den då behovet uppstår medför det till ett mer hållbart energisystem. Flödesbatterier är en möjlig teknik för lagring av energi. En viktig komponent i flödesbatterierna är vanadin och att hitta metoder för att utvinna vanadin på ett ekonomiskt sätt är ett viktigt steg i utvecklingen av denna teknik. Idén bakom examensarbetet var därför att kartlägga olika utvinningsmetoder för vanadin där de mest lovande metoderna, från ett ekonomiskt och energi perspektiv, undersöks mer utförligt. Vanadinet i sin tur ska sedan användas till elektrolyt i flödesbatterier. Det har även undersökts hur kostnaden påverkas av att flytta en tänkt anläggning för utvinning ur aska till ett utvecklingsland med lägre personalkostnader. I examensarbetet ingick även att undersöka liknande projekt i större skala som bedrivits i Sverige, hur synen på vanadin är ur ett EU perspektiv samt hur flödesbatterier kan vara en del av ett energisystem. De metoder som ansetts mest lovande är utvinning från mineralbrytning samt utvinning ur aska. En tänkt produktionsanläggning har dimensionerats för båda processer där produktionskostnad och energiförbrukning beräknats. Studien visade att båda processerna förväntas kunna producera vanadin under dagens inköpspris vilket då skulle bidra till en billigare produktionskostnad för flödesbatterier. Det visade sig att produktionen av vanadin ur askutvinning skulle minskas avsevärt genom att flytta verksamheten till ett utvecklingsland. Det moment i gruvdriften som står för största energiförbrukningen är storleksreduceringen av den malm som bryts. Vid processen för utvinning av vanadin ur aska är det främst den smältningsugn samt det filter för flygaska som krävs. De liknande projekt som verkat inom utvinning ur aska var den s.k. SOTEX processen i Stenungsund och för mineralbrytning har Ranstad projektet undersökts. EU:s syn på vanadin är i nuläget att metallen inte klassas som en kritisk råvara men om ekonomisk instabilitet skulle uppstå i något av de större tillverkande länderna skulle råvaran klassas som mer kritisk. Flödesbatteri fungerande som energilagring i ett förnyelsebart energisystem undersöktes där slutsatsen var att flödesbatterier tekniskt sett är mycket väl lämpade som energilagring i denna typ av system.

Th.--Sci. phys.--Paris 6, 1977.

The scientific relevance and potential for technological applications of complex materials have made them the focus of active investigation in order to fully charac- terize the competition and interactions between their electronic, structural, orbital, and spin degrees of freedom. Optical and terahertz (THz) spectroscopy provide ac- cess to electronic and low frequency quasiparticle responses, and therefore play a key role in understanding the fundamental mechanisms which dictate the macroscopic properties of complex materials. Time-resolved experiments, in turn, have the po- tential to disentangle the various coexisting energy scales through a careful selection of the pump and probe characteristics. This work investigates the role played by the electronic, structural and magnetic excitations in the insulator-to-metal transi- tions (IMT) of VO2, V2O3 and NdNiO3, through studies under different conditions of temperature, strain, doping and photoexcitation. Our work shows that a complete understanding of the IMT in VO2 requires sev- eral length scales and time scales to be considered. Indeed, epitaxial strain leads to anisotropy in the IMT characteristics of thin films of (100) and (110) VO2/TiO2, measured using THz spectroscopy, which can be explained by strain induced modi- fications both in the (microscopic) V3d orbitals and in the geometry of mesoscopic metallic domains. On the other hand, ultrafast studies which track, with femtosecond resolution, the electronic and structural dynamics of VO2 thin films following THz excitation reveal a delay in the onset of the structural response with respect to the electronic one, lending support to the correlation rather than Peierls driven picture of the IMT in this material. As for V2O3, the IMT is seen to occur via nucleation and growth of metallic domains, as previously reported in VO2. However, a scaling of the photoinduced conductivity dynamics rise time is further identified, which reveals the temperature and fluence dependence of the nucleation and growth process. Finally, strained NdNiO3 films exhibit a two step dynamical conductivity response following optical excitation, different from that of the vanadates with which they share a complex, albeit more tunable, phase diagram. This hints at a significant role being played by the magnetic structure during the IMT in NdNiO3.

Dans cette étude, nous proposons des procédures basées sur des calculs informatiques et des modèles théoriques qui peuvent être utilisés pour prévoir le comportement de certains matériaux membranaires d'intérêt pour les applications de séparation de gaz. En particulier, nous nous sommes concentrés sur: i) des alliages VNiTi de structure cubique centrée, considérés comme de nouveaux matériaux pour les membranes denses sélectives à H2 et ii) sur des matériaux poreux cristallins qui sont des systèmes attractifs pour la séparation de gaz légers tels que H2, O2, CO, CO2, CH4 et N2. Les deux groupes de matériaux sont traités en utilisant une méthodologie différente, adaptée aux besoins des recherches associées à ces matériaux.Dans le cas des membranes métalliques denses, nous nous sommes intéressés à la controverse, connue de longue date, concernant l'occupation de l'hydrogène interstitiel dans les alliages à base de vanadium. Le système V-Ni-Ti est en effet particulièrement intéressant grâce à sa perméabilité élevée pour H2 et à ses propriétés mécaniques accrues par rapport au vanadium pur. Ce travail cible la compréhension de la structure ces alliages à l'échelle atomique, de façon à les optimiser et à activer la conception et le développement de ces matériaux comme nouvelles membranes pour la séparation de H2. Notre approche, basées sur les premiers principes, donne un aperçu des sites préférentiels de l'hydrogène et évalue le rôle des solutés de substitution Ti et Ni, sur l'affinité d'absorption de l'hydrogène. La méthode basée sur la théorie de la fonctionnelle de la densité (DFT) ne nécessite aucune donnée expérimentale autre que l'information sur la structure cristalline. En outre, cette méthode n’utilise aucun paramètre empirique ou d’ajustement, contrairement à d'autres techniques de calcul. Ainsi, cette approche est une voie alternative pour explorer de nouveaux alliages métalliques utilisables comme membranes de séparation de H2. La méthodologie appliquée pourra être utilisé ensuite dans des calculs à haut débit pour cribler diverses compositions d'alliage. Les résultats reportés ici seront utilisés comme guide pour adapter la formulation des solutions solides VNiTi et préparer des membranes en alliage denses à faible coût (par rapport aux membranes à base de palladium) dans le cadre d’autres projets (e.g. Projet Européen FP7- DEMCAMER).Dans le cadre de notre étude sur les membranes cristallines microporeuses, nous démontrons comment les données sur un composant unique peuvent être utilisées pour prédire la sélectivité idéale de ces membranes envers les gaz légers. Des modèles théoriques sont ainsi proposés pour décrire les propriétés de séparation de gaz de matériaux de type zéolithiques (« zeotypes ») en fonction de leurs paramètres structuraux et des conditions de fonctionnement. Les paramètres du modèle peuvent être obtenus expérimentalement ainsi que par le calcul. Afin d’analyser le degré de validité et les limites des modèles, les sélectivités idéales de deux membranes zéolithes classiquement étudiées (NaA, CaA) et d’une membrane MOF (ZIF-8) ont été évaluées. Les résultats démontrent que les expressions théoriques peuvent être utilisées pour le criblage de séries de matériaux microporeux cristallins sous réserve que des données fiables sur l'adsorption de gaz purs soient disponibles pour ces matériaux. Cependant, étant donné que les modèles n’intègrent pas tous les paramètres (notamment liés au design des membranes) et mécanismes impliqués dans le transport de gaz à travers ces membranes, les prédictions doivent être considérées comme celles correspondant à un cas idéal. / In this study, we propose procedures based on computational calculations and theoretical models that can be used to predict the behaviour of some of the membrane materials of interest for gas separation applications. In particular, we focus on: i) body-centred cubic VNiTi alloys as novel materials for H2-selective dense membranes and ii) crystalline porous materials that are attractive media for separation of light gases such as H2, O2, CO, CO2, CH4 and N2. These two types of materials are treated using different methodologies, adapted to the needs of our research objectives associated to each material.In the case of dense metal membranes, the long-standing controversy over occupancy of interstitial hydrogen in V-based alloys is addressed. The V-Ni-Ti system is of particular interest here, exhibiting high H2 permeability and improved mechanical properties relative to pure V. This work intends to gain understanding of hydrogen-metal interactions as function of alloy composition and thereby to optimize these new materials and advance their development as novel membranes for H2 separation. We use a first-principles approach that gives insights into the sites preference of hydrogen and assesses the role of Ti and Ni substitutional solutes for the hydrogen absorption affinity. The method based on Density Functional Theory requires no experimental input except crystal structure information. Furthermore, it uses no empirical or fitting parameters in contrast to other computational techniques. Hence this approach provides an alternative way to explore new metal alloys for H2 separation membranes. The applied methodology can be used further in high-throughput calculations to screen various alloy compositions. The hereto-reported results will be used as guidance for tailoring the formulation of VNiTi solid solutions and preparation of low cost dense alloy membranes in the frame of other projects (e.g. European DEMCAMER project).Further, we explore how single-component inputs can be used to forecast the ideal selectivity towards light gases of crystalline porous materials, used for membrane preparation. Theoretical models for describing gas separation properties of zeotype materials as function of structural characteristics and operation conditions are proposed. The model parameters can be obtained as experimentally as well as computationally. To analyse the extent of validity and limitations of the models, ideal selectivities of few crystalline porous materials are evaluated, including widely used zeolites (NaA, CaA) and a metal organic framework structure (ZIF-8). The results verified that the theoretical expressions could be used for screening series of zeotype materials when reliable single gas adsorption data are available. However, since the models don’t take into account all parameters (namely related to the membrane design) and mechanisms involved in gas transport through porous membranes, their predictions should be considered as values referring to an ideal case.