Nanoparticles represent a very exciting new area of research. Their small size, ranging from several nanometers to tens of nanometers, is responsible for many changes in the structural, thermal, electromagnetic, optical and mechanical properties in comparison with the bulk solid of the same materials. However, promoting the use of such material requires well-controlled synthesis techniques to be developed. Inductively coupled thermal plasma (ICTP) reactors have been shown to offer unique advantages over other synthesis methods. The purpose of this thesis is to develop a numerical model to assist the design of an ICTP reactor for the efficient and controlled production of nanoparticles at industrial scale. The complete model describes the evaporation of the micron-sized precursor particles in the plasma flow and the subsequent formation of the nanoparticles in the quenching reactor. The plasma flow is described by a coupled system of the fluid mechanics equations of continuity, momentum, and energy with the vector potential formulation of Maxwell's equations. The solid particles precursors are treated following a Lagrangian approach, taking into account the vapor production field in the plasma flow. An Eulerian model based on the method of moments with interpolative closure is used to describe the formation of nanoparticles by simultaneous nucleation and growth by condensation and coagulation. The coupled plasma torch, particle evaporation and nanoparticle formation models are implemented in 2D and 3D configurations, using the OpenFoam source code. The results show that the effects of the particle evaporation on the temperature field are substantial, even for low particle mass loading. The associated vapor concentration which enters in the reactor has then a direct influence on the formation of nanoparticles. The effects of the plasma torch parameters and the quenching configuration (quench type, position, injection angle and cooling rate) on the contribution of the different formation mechanisms and on the generated particle's size and distribution are studied in both 2D axi-symmetric and 3D geometries. The quench mechanism strongly affects the temperature and the vapor concentration in the reactor, and consequently has an impact on the final particle size distribution. It is shown that the size of the nanoparticles obtained for different quenching conditions is not only a consequence of the cooling rate but also of the trajectories of the vapor and the generated particles imposed by quenching gas. The results have also demonstrated that the predicted particle are smaller and more sensitive to the modifications of the quenching condition when quenching at high temperature. The sensitivity of the complete model to the physical properties of the vapor (vapor pressure and surface tension) is also investigated, in order to identify their effect on the final particle size. The results obtained provide an insight into the phenomena involved during the production of nanoparticles and enable the improvement of ICTP rectors design and nanoparticles synthesis process. / Doctorat en Sciences de l'ingénieur et technologie / info:eu-repo/semantics/nonPublished

Alzheimer's disease (AD) is characterised by a series of biomolecular aggregation events, which include the formation of neurotoxic protein structures composed of the β-amyloid (Aβ) peptide. In this thesis, fluorescence self-quenching (FSQ) between fluorescently-labelled peptides is introduced as a strategy for detecting and characterizing Aβ aggregates in solution, and for overcoming limitations associated with conventional methods. Using a combination of steady-state, picosecond time-resolved fluorescence and transmission electron microscopy, the fluorescence response of HiLyte Fluor 555-labelled Aβ peptides is characterised to demonstrate that Aβ self-assembly organizes the covalently attached probes in close proximity to trigger the self-quenching sensing process over a broad range of conditions. Importantly, N-terminal tagging of β-amyloid peptides is shown to not alter the self-assembly kinetics or the resulting aggregated structures. When performed in Förster resonance energy transfer (FRET) format, this method becomes a ratiometric platform to gain insights into amyloid structure and for standardizing in vitro studies of amyloid self-assembly. The ability of FSQ-based methods to monitor the inhibition of Aβ aggregation by model test compounds including the small heat shock protein (Hsp), the amyloid-binding alcohol dehydrogenase protein (ABAD) and bovine serum albumin (BSA) is also demonstrated. Given that Aβ is formed within the cell membrane and is known to induce its disruption, sophisticated single-molecule fluorescence spectroscopy methods were developed to quantify membrane dynamics induced by the presence of disrupting agents, such as Aβ and detergents. The solubilisation dynamics of single liposomes induced by the non-ionic surfactant Triton-X 100 (TX-100) were studied in real-time. Using this approach, the swelling and permeabilization steps of the solubilisation process were unambiguously separated within single FRET trajectories, and their kinetic details as a function of Triton-X 100 and presence of cholesterol within the membrane structure were examined. Finally, single-molecule stepwise-photobleaching techniques were employed to study the effect of Aβ oligomers interacting with supported-lipid bilayers, establishing a platform from which to investigate how the presence of a membrane layer affects Aβ oligomerization at the level of individual molecules. Overall, the fluorescence-based strategies for amyloid- and liposome-sensing presented in this work bridges the gap between current morphology-specific techniques and highly-specialized single-molecule methods to provide a biophysical toolbox to investigate the changes in structure, size and molecular interactions accompanying the amyloid aggregation pathway and for the screening of novel therapeutic and diagnostic agents.

L’imagerie fonctionnelle cérébrale détecte les changements hémodynamiques induits par un stimulus pour déterminer les zones d’activation neuronale. Plus particulièrement, l’imagerie BOLD en IRMf détecte les changements d’oxygénation du sang grâce aux propriétés paramagnétiques de la déoxyhémoglobine. L’oxygène n’est donc pas uniquement un substrat énergétique pour le tissu neuronal, il joue également un rôle majeur dans l’imagerie noninvasive du cerveau humain. Au cours de ma thèse, j’ai tout d’abord participé à la mise au point d’une nouvelle technique non-invasive d’imagerie de l’oxygène dans le cerveau d’animaux anesthésiés. Couplant un nouveau senseur phosphorescent de l’oxygène (Finikova et al., 2008) et la microscopie biphotonique, cette approche permet à la fois de cartographier l’oxygène en 3D avec une résolution spatiale et temporelle jusqu’alors inégalée, mais aussi de suivre simultanément l’oxygène et le flux sanguin dans les capillaires cérébraux au repos ou lors d’une activation neuronale (Lecoq et al., 2011). Tirant profit des nouvelles possibilités de cette technique, nous avons alors démontré: • la présence d’un shunt artério-veineux uniquement basé sur la diffusion de l’oxygène. Ce résultat, obtenu chez le rat dans la couche la plus superficielle du bulbe olfactif: la couche du nerf (ONL), confirme que l’oxygène ne diffuse pas uniquement à partir des capillaires et démontre que les artérioles contribuent significativement à l’oxygénation du tissu cérébral. Il démontre également qu’il n’est pas possible de déterminer ni la Po2 capillaire ni la Po2 tissulaire à partir de la Po2 veineuse. • l’existence de transitoires de Po2 associés à chaque globule rouge dans le compartiment capillaire, appelés EATs (erythrocyte-associated transients) (Hellums, 1977; Cabrales and Intaglietta, 2007). En bref, de part leur diamètre supérieur à celui de la lumière d’un capillaire, les globules rouges passent un à un dans la lumière des capillaires, laissant entre eux un espace de plasma. Cependant, la faible solubilité de l’oxygène dans le plasma crée une barrière à la diffusion, ce qui se traduit par une inhomogénéité de la Po2 capillaire: celle-ci est élevée au bord du globule rouge et décroit avec la distance pour atteindre un minimum à mi-distance entre deux globule rouges. Poursuivant l’étude des EATs (Parpaleix et al., 2013), nous avons observé les points suivants: • La Po2 tissulaire dans l’environnement immédiat d’un capillaire peut être déterminée à partir de la Po2 vasculaire à mi-distance entre deux érythrocytes. Ce résultat est intéressant en ce qu’il permettra d’effectuer des mesures non invasives de Po2 tissulaire, utile notamment chez l’animal éveillé. • L’amplitude des EATs est si large (35 mmHg en moyenne) que la Po2 capillaire moyenne ne reflète en rien la saturation en oxygène de l’hémoglobine. • Une empreinte filtrée des EATs vasculaires est détectable dans le tissu (_5 mmHg d’amplitude). • Au cours d’une stimulation neuronale, une diminution de la Po2 capillaire moyenne peut être détectée avant l’hyperémie fonctionnelle, un résultat jusqu’à présent controversé dans le domaine de l’imagerie BOLD en IRMf, mais important en ce que ce dip pourrait être un rapporteur très résolutif de l’activation neuronale. Parmi les questions restant en suspens et pouvant être étudiées finement avec notre approche, j’en citerai une principale: quel est le poids des différents facteurs (métaboliques, présynaptiques ou post-synaptiques) et du flux sanguin dans l’établissement de la Po2 cérébrale au repos? / In humans, functional mapping of brain activity mainly relies on the increase of cerebral blood flow (CBF) triggered by neuronal activation. This neurovascular coupling provides energy substrates such as oxygen and glucose to the activated area. The steady state concentration of oxygen, as well as its dynamics upon neuronal activation, have been investigated with numerous methods, however, none of them provided highly resolute measurements in depth. During my PhD, we combined a phosphorescence quenching approach with two-photon microscopy to detect, in depth and with a micrometer spatial resolution scale, the emission of phosphorescence by PtP-C343, a new oxygen nano-sensor designed for two-photon excitation. We first characterized the technique and then reported two biological results, using the olfactory bulb (OB) glomerulus as a model to study oxygen concentration, at rest and upon odor stimulation. We found an arterio-venous shunt, purely based on diffusion, in the superficial nerve layer of the OB, confirming the role of arterioles in brain oxygenation. Simultaneous measurements of Po2 and blood flow allowed us to reveal the presence of erythrocyte-associated transients (EATs), i.e. Po2 fluctuations that are associated with individual erythrocytes. Pursuing the investigation of EAT characteristics, we found that in capillaries, Po2 at mid-distance between two erythrocytes is at equilibrium with, and thus reports Po2 in the nearby neuropil. Finally, we could observe that even in capillaries, a small oxygen initial dip can be detected prior to functional hyperemia, upon odor activation.

Abstract The effect of austenite pancaking in the non-recrystallisation regime on microstructure and mechanical properties, especially bendability, was investigated in direct-quenched ultrahigh-strength strip steels with martensitic-bainitic microstructures. Lowering the finishing rolling temperature (FRT) increased total reduction in the non-recrystallisation region (R tot). Niobium microalloying increased Rtot while variations in C, Mn and Mo did not affect Rtot to the same extent as Nb. A decrease in the FRT increased the incidence of softer microstructures such as ferrite and granular bainite in the subsurface layers. The microstructures at the centreline were comprised of auto-tempered martensite with some bainite. An increase in Rtot strengthens the intensities of the ~{554}<225>α and ~{112}<110>α texture components at the centreline and the components ~{112}<111>α and ~{110}<112>α - {110}<111>α at the strip subsurface. Bendability is poorer with the bend axis perpendicular rather than parallel to the rolling direction (RD) and is further impaired with increasing hardness below the sheet surface. An intense ~{112}<111>α shear texture combined with upper bainite containing MA islands in the subsurface region is shown to be detrimental to bendability when the bend axis is perpendicular to the RD. This anisotropy of bendability can be explained by the appearance of geometric softening in grain clusters belonging to this texture component when the bend axis is perpendicular to the RD. Shear localisation is prevented, however, by the presence of a sufficiently thick subsurface microstructure having adequate work hardening capacity, i.e., ferrite + granular bainite rather than ferrite + upper bainite. The strain required to initiate strain localisation can be increased and good bendability thereby achieved—even in the presence of detrimental texture components—by ensuring the presence of a sufficiently soft subsurface layer extending to a depth of approximately 5% of the total sheet thickness. The above beneficial microstructures can be obtained and good bendability ensured in direct-quenched strip steel with a yield stress above 900 MPa together with good impact toughness, provided a suitable combination of chemical composition and processing parameters is selected and sufficient attention is paid to steelmaking operations to obtain a proper inclusion structure. / Tiivistelmä Austeniitin muokkauksen vaikutusta mikrorakenteeseen ja mekaanisiin ominaisuuksiin, erityisesti särmättävyyteen, tutkittiin suorasammutetuilla martensiittis-bainiittisilla suurlujuusnauhateräksillä. Kuumavalssauksen lopetuslämpötilan lasku kasvatti austeniitin kokonaisreduktiota ei-rekristallisaatioalueella. Mikroseostus niobilla kasvatti myös kokonaisreduktiota, kun taasen muutokset C-, Mn- ja Mo -pitoisuuksissa eivät vaikuttaneet yhtä voimakkaasti. Valssauksen lopetuslämpötilan lasku kasvatti pehmeämpien mikrorakenteiden, kuten ferriitin ja granulaarisen bainiitin, määrää nauhan pintakerroksessa. Terästen keskilinjan mikrorakenteet koostuivat pääasiassa itsepäässeestä martensiitista sekä pienestä määrästä bainiittia. Kokonaisreduktion kasvu voimisti ~{554}<225>α - ja ~{112}<110>α -tekstuurikomponentteja keskilinjalla sekä ~{112}<111>α- ja ~{110}<112>α - {110}<111>α -komponentteja nauhan pintakerroksessa. Särmättävyys oli huonompi särmän ollessa poikittain valssaussuuntaan nähden kuin pitkittäin. Pintakerroksen kovuuden kasvu heikensi särmättävyyttä. Pintakerroksen voimakas ~{112}<111>α -leikkaustekstuuri, yläbainiitin ja MA-saarekkeiden läsnä ollessa, osoittautui haitalliseksi särmän ollessa poikittain valssaussuuntaan nähden. Särmättävyyden anisotrooppisuus voidaan selittää geometrisella pehmenemisellä rakeissa, joissa kyseinen tekstuurikomponentti on voimakas. Leikkausmyötymän paikallistuminen estyy, kun pinnassa on riittävän paksu hyvän muokkauslujittumiskyvyn omaava kerros, mikä sisältää esim. ferriittiä ja granulaarista bainiittia, mutta ei ferriittiä ja yläbainiittia. Särmättävyys osoittautui pysyvän hyvänä huolimatta haitallisesta tekstuurikomponentista, kun pehmeä pintakerros ulottui noin 5 % syvyydelle levyn paksuudesta. Edellä mainitut mikrorakenteet ja hyvä särmättävyys voidaan saavuttaa suorasammutetuilla yli 900 MPa myötölujuuden nauhateräksillä yhdessä hyvän iskusitkeyden kanssa, kunhan valitaan sopiva kemiallisen koostumuksen ja valmistusparametrien yhdistelmä sekä kiinnitetään huomiota teräksen sulkeumapuhtauteen.

Les procédés de trempe sont largement répandus dans l'industrie en particulier dans le domaine de l'automobile, du nucléaire et de l'aérospatiale car ils ont un impact direct sur la microstructure, les propriétés mécaniques et les contraintes résiduelles de pièces critiques. La trempe est un processus fortement non-linéaire à cause des couplages forts entre la mécanique des fluides, les transferts thermiques aux différentes interfaces, les transformations de phase du solide et l'ébullition du milieu de trempe. Malgré les progrès effectués par la simulation numérique, ce procédé reste extrêmement difficile à modéliser.Dans ce travail, nous proposons le développement d'outils numériques permettant la simulation réaliste de ce procédé à l'échelle industrielle. La mécanique des fluides est simulée en utilisant une méthode d'Elements Finis stabilisés permettant de considérer des écoulements à haut nombre de Reynolds. Les transferts thermiques sont calculés directement sans l'utilisation de coefficients de transferts empiriques, en utilisant le couplage fort entre le fluide et le solide. Nous avons développé un modèle de changement de phase pour l'eau permettant de considérer les différents régimes d'ébullition. Une formulation unifiée des équations de Navier-Stokes, considérant une phase compressible et une phase incompressible a été développée afin de prendre en compte plus précisément la dynamique de la vapeur et de l'eau. Une procédure dynamique d'adaptation anisotrope de maillage, permettant une description plus fine des interfaces et une prise en compte plus précise des caractéristiques des écoulements est utilisée.Des exemples numériques exigeants ainsi qu'une validation expérimentale permettent d'évaluer la précision et la robustesse des outils proposés.Les outils développés permettent ainsi l'optimisation du mode opératoire du procédé, des ressources consommées et servent ainsi d'outils prospectifs pour la conception de produits. / Quenching processes of metals are widely adopted procedures in the industry, in particular automotive, nuclear and aerospace industries, since they have direct impacts on changing mechanical properties, controlling microstructure and releasing residual stresses of critical parts. Quenching is a highly nonlinear process because of the strong coupling between the fluid mechanics, heat transfer at the interface solid-fluid, phase transformation in the metal and boiling. In spite of the maturity and the popularity of numerical formulations, several involved mechanisms are still not well resolved.Therefore we propose a Direct Numerical Simulation of quenching processes at the industrial scale dealing with these phenomena. The fluid mechanics is simulated using a Finite Element Method adapted for high convective flows allowing the use of high stirring velocity in the quenching bath. Heat transfers are computed directly without the use of heat transfer coefficients but using the strong coupling between the fluid and the solid. We use a phase change model for the water that models all boiling regimes. A unified formulation of the Navier-Stokes equations, taking into account a compressible gas and an incompressible liquid is developed to model more accurately the vapor-water dynamics. A dynamic mesh adaptation procedure is used, increasing the resolution in the description of the interfaces and capturing more accurately the features of the flows.We assess the behavior and the accuracy of the proposed formulation in the simulation of time-dependent challenging numerical examples and experimental results.These recent developments enable the optimization of the process in terms of operating conditions, resources consumed and products conception.

In this thesis resonance energy transfer between perylene and fluorescein in tetradecyltrimethylammonium bromide (TTAB) solution was studied. The influence of addition of native or modified sodium hyaluronate on resonance energy transfer was also investigated. The addition of native sodium hyaluronate supports energy transfer at lower fluorescein concentrations and the addition of modified sodium hyaluronate influences the maximal value of energy transfer effectivity. Strong influence on the critical micelle concentration (CMC) values with the addition of sodium hyaluronate during CMC of TTAB determination was investigated. The data indicates not only micelles formation, but also formation of aggregates of sodium hyaluronate with TTAB. Aggregation numbers of TTAB with addition of native and modified sodium hyaluronate by the quenching of pyrene by cetylpyridinium chloride (CPC) was investigated. The addition of sodium hyaluronate into the solution of TTAB changes the average mean aggregation number. Solute exchange between micelles of TTAB and the influence of addition of modified sodium hyaluronate on this exchange was also investigated. No solute exchange between micelles in TTAB and in TTAB with added modified sodium hyaluronate was discovered during this experiment.

Heat treatment influences structure and characteristics of treatmented material. Good heat treatment of steels for bearings ensures hardness of matrix 60 - 65 HRC, whereas structure has be formed by tempered fine needle-shaped martensite with definite part of residual austenite. Carbides should be evenly dispersed, they mustn´t create carbide network and carbide lines. Quality of steels for bearings is also influenced by volume and morphology of inclusions in the matrix. In this diploma thesis various conditions of heat treatment were to be set up with the aim of choose the optimal ones. These ensures perfect martensite transformation and full hardening of all component. Quenching from 760 °C – 770 °C was quite unsatisfactory. At this temperature resulting structure was ferritic-perlitic, because martensite transformation did not pass. Too long hold on hardening temperature also had unfavourable influence on resulting structure and characteristics. In this case, structure was created by very coarse needle-shaped martensite. Coarsening of martensite needle locally exceeded maximum allowed level. In the structure there was also possible to watch partly soluted globular carbides. Optimal heat treatment is quenching from 850 °C – 870 °C followed by tempering at 220 °C. Resulting structure quite agree with above-mentioned needs. This heat treatment can be recommended for technical practise.

This thesis deals with the properties of ledeburitic chrome-vanadium tool steel after heat treatment. Theoretical part contains charakterization of ledeburitic steels, the posibility of manufacturing and heat treatment. There are also briefly describes the principles of the test methods, which were used. The practical part is focused on describing the results of 12 sample groups, with different heat treatment. The results are compared in the final discussion.

This master thesis deals with the interaction of humic acids with organic ions and effect of chemical modification of humic acids on this interaction. Rhodamine 6G was used as a model organic ion. The interaction were studied by fluorescence quenching, dialysis in diffusion cells and differential UV-VIS spectroscopy. Results showed that the bond between the reactants was not primarily dependent on carboxylic functional groups of humic acids. Fluorescence experiments indicated static quenching mechanism and differential UV-VIS spectroscopy demonstrated the existence of - interactions.

Sous irradiation, les flux de particules (neutrons, ions, électrons) créent des défauts ponctuels (lacunes et interstitiels) qui génèrent des défauts étendus (boucles de dislocation, cavités) responsables de la fragilisation des matériaux. L'aluminium est un matériau de faible masse et de faible énergie seuil de déplacement (Ed=16-19 eV) ce qui permet de créer les nanodéfauts étendus directement sous irradiation aux électrons dans un microscope électronique à transmission haute résolution (HRMET). Cet instrument permet non seulement de caractériser finement les nanodéfauts mais également d'étudier leur évolution in situ sous irradiation, ceci en fonction de la température, du taux de dommage et d'une pression partielle d'hydrogène. Nous avons constaté un effet important de la pression partielle d'hydrogène sur la cinétique de formation des boucles de dislocation et des cavités. Parallèlement, nous avons mis en place une modélisation multi-échelle des effets de taille finie et de discrétisation du réseau sur la morphologie d'équilibre des cavités à partir de calculs ab initio des énergies de surface et de liaison de petits amas lacunaires et des amas mixtes lacune-hydrogène. La caractérisation expérimentale des morphologies des cavités en fonction de leur taille met en évidence trois formes régulières : une forme de croix bordée par des surfaces {100}, une forme d'octaèdre non tronqué bordée par des surfaces {111} et une forme d'octaèdre tronqué, bordée par les surfaces {111} et {100} ainsi qu'un effet de taille finie entre ces formes prédit par le modèle. De même, la mesure des fluctuations morphologiques d'une cavité au cours de sa croissance ou de sa décroissance en taille révèle le rôle déterminant des nombres magiques fixés par la géométrie et la discrétisation du réseau. A partir du modèle thermodynamique des cavités et d'une caractérisation expérimentale de la densité volumique et de la distribution en taille des nanodéfauts, nous proposons un modèle de germination des cavités sous irradiation. Nous en déduisons une taille du germe critique et un taux de germination des cavités en fonction de la température et du taux de dommage, qui sont comparés aux valeurs expérimentales correspondantes extraites des observations in situ. Enfin, nous discutons de l'effet de l'hydrogène sur la stabilité des amas mixtes lacune-hydrogène et sur la cinétique de germination des cavités. / Under irradiation, flows of particles (neutrons, ions, electrons) induce ponctual defects (vacancies and interstitials) which generate extended defects (dislocation loops, cavities) that are responsible for materials weakening. Aluminum is a low mass material with a low displacement energy (Ed=16-19 eV) which allows the creation of extended defects directly under electron irradiation in a high resolution transmission electron microscope (HRTEM). This instrument allows not only a fine characterization of nanodefects but also to study their evolution in situ under irradiation, depending on temperature, damage rate and a partial pressure of hydrogen. We noticed an important effect of the hydrogen partial pressure on the kinetic of formation of the cavities and dislocation loops. Simultaneously, we developped a multiscale modelisation of finite size effets and structure discretisation on equilibrium shapes of cavities based on binding and surface energies determined by ab initio calculation of small vacancy clusters and mixted hydrogen vacancy clusters. Experimental characterization of cavity shapes according to the cavity radius reveals three regular shapes : a cross shape bounded by {100} surfaces, an octahedral non-truncated shape bounded by {111} surfaces and an octahedral truncated shape, bounded by {100} and {111} surfaces as well as the determination of a finite size effect predicted by the model. Also, measurements of cavity shape dispersion during its growth and decrease showed a dominant effet of magic numbers, fixed by geometry and frustration of the structure. Based on a thermodynamic model and a fine experimental characterization of volumic density, we propose a nucleation model of cavities under irradiation. We deduce from this model a critical cluster size and a rate of cavity nucleation depending of temperature and damage, which are compared to the corresponding experimental values extracted from in situ observations. Finally, we discuss the effect of hydrogen on the stability of vacancy-hydrogen clusters and on the kinteic of cavity nucleation.