Abstract In this thesis, methods to process ultrafine ferritic (UFF) structures in steels, i.e. grain sizes below about 3 μm have been investigated. It is shown here, in accordance with the results in the literature, that a steel with a UFF grain size can be obtained by two methods, more or less convenient to mass production: deformation-induced ferrite transformation from fine-grained austenite (the DIF route) and the static recrystallization of various heavily cold-worked initial microstructures (the SRF/SRM route). In the present work, the influencing factors in the processing of UFF structure in the DIF route have been systematically studied in four low-carbon steels: one C-Mn steel and Nb, Nb-Ti and Nb-high Ti microalloyed steels. A high strain, a low deformation temperature close to Ar3 and a fine prior austenite grain size are beneficial to promote the formation of UFF grains. Especially by using complex pretreatments to refine the prior austenite grain size, cold rolling, repeating the low-temperature reheating cycle or using martensitic initial microstructure, a UFF grain size can be obtained in these steels at the strain of 1.2 (70% reduction) at 780 °C. By controlling the cooling rate, the type of the second phase can be adjusted. When using the static recrystallization route, it was found that UFF is difficult to obtain from a single-phase ferrite, but it is relatively readily obtained from deformed pearlite, bainite or martensite, especially in high-carbon steels with 0.3–0.8%C. In deformed pearlite, the cementite lamellae fragmented and spheroidised in the course of heavy deformation can provide numerous nucleation sites by the particle stimulated nucleation mechanism and retard the subgrain and recrystallized grain growth. Nucleation and retardation of grain growth are effective also in deformed bainite, martensite or high-carbon tempered martensite, as discussed in detail in the work. The thermal stability of UFF grained steels was tested and found to be generally excellent, but it varies depending on the processing method. The UFF structure obtained by the SRM route has a thermal stability somewhat weaker than that of the DIF route. For a given steel, UFF grains may show different grain growth modes, related to the dispersion of second phase particles. In the DIF structure, abnormal grain growth occurs at 700 °C after about 2.5 h, while in the SRM structure, normal grain growth takes place slowly at 600 °C. Carbides on the grain boundaries seem to play an important role in inhibiting grain coarsening. No coarse-grained zone was formed at the HAZ of electron beam or laser welded seams, as performed at low heat inputs (up to 1.5 kJ/cm) on thin strips. The hardness even increased from the base metal towards the HAZ and the weld metal in all seams as an indication that they were hardened during the rapid cooling.

Afin de développer des capteurs ultrasensibles des substrats fiables pour la diffusion Raman exaltée de surface (SERS) ont été fabriqués. Les deux meilleurs candidats de matériaux constituant les nanoparticules pour des substrats SERS sont l’argent et l’or. L’argent présente un meilleur facteur d’exaltation de l'intensité Raman et l’or est stable dans les milieux biologiques. C’est pourquoi la combinaison de ces deux métaux dans des nanostructures bimétalliques semble être une approche prometteuse qui combine les propriétés de surface de l’or et d’exaltation de l’argent. Le recuit thermique des couches métalliques minces est utilisé comme une technique simple et peu coûteuse. Cette dernière permet d’élaborer des substrats homogènes et reproductibles de nanoparticules bimétalliques or-argent ayant un facteur d’exaltation importante. Ces nanoparticules gardent leurs propriétés d’exaltation même après une année de fabrication. En jouant sur la composition de nanoparticules bimétalliques il est possible d’avoir une résonance de plasmons de surface localisés (LSPR) sur tout le spectre visible. Ces substrats sont caractérisés par une exaltation SERS supérieure lorsque la résonance plasmon est plus proche de la longueur d'onde d'excitation Raman. En outre, les nanoparticules bimétalliques de différentes tailles, compositions ont été réalisés par lithographie électronique. L’étude systématique de leurs propriétés plasmoniques et de leur exaltation SERS a révélé une conservation du lien entre résonance plasmon et signal SERS / Driven by the interest in finding ultrasensitive sensors devices, reliable surface enhanced Raman scattering (SERS) based substrates are fabricated. Silver and gold nanoparticles are two of the best candidates for SERS substrates where Ag nanoparticles exhibit large enhancing ability in Raman intensity while Au nanostructures are stable in biological systems. Hence, combining the two metals in bimetallic nanostructures appeared to be a promising approach in order to sum the merits of Au surface properties and Ag enhancing ability. Thermal annealing of thin metallic films is used as a simple and relatively inexpensive technique to elaborate homogenous and reproducible Ag/Au bimetallic nanoparticles SERS substrates with high enhancing ability. The fabricated nanoparticles proved their enhancing stability even after one year of fabrication. Manipulating the composition of Ag/Au bimetallic NPs resulted in tuning the Localized Surface Plasmon Resonance (LSPR) over the whole visible spectrum, where the substrates are characterized with higher SERS enhancement when they exhibit LSPR closer to the Raman excitation wavelength. Additionally, bimetallic nanoparticles patterns with different size, composition and lattice constants have been conducted by electron beam lithography. The systematic study of their interesting plasmonic and SERS enhancing properties revealed maintenance in the LSPR-SERS relation by changing the nanoparticle size

Magnesiumwerkstoffe sind aufgrund ihrer geringen Dichte und hohen spezifischen Festigkeit für den Leichtbau prädestiniert. Ziel der vorgelegten Arbeit ist es, durch die gleichzeitige Verbesserung des Korrosions- und Verschleißverhaltens neue Anwendungsfelder für Magnesiumlegierungen zu erschließen. Anhand der Magnesiumlegierung AZ91D wurden die Möglichkeiten einer lokalen beanspruchungsgerechten Modifikation von Struktur und Gefüge im oberflächennahen Bereich durch eine Elektronenstrahl(EB)-Flüssigphasen-Randschichtbehandlung ohne Zusatzstoff (EB-Umschmelzen) und unter Verwendung von Al-Si-Zusatzstoffen (EB-Umschmelzlegieren) aufgezeigt. Die mittels verschiedener hochfrequenter Strahlablenktechniken erzeugten Schichten weisen eine deutliche Gefügefeinung, neue Gefügemorphologien sowie eine veränderte Phasenverteilung und/oder -neubildung auf, sind riss- und porenfrei und haben eine ausgezeichnete schmelzmetallurgische Anbindung an den Grundwerkstoff. Anhand von Tauchversuchen und potentiodynamischen Polarisationsmessungen in verschieden konzentrierten NaCl-Lösungen konnte eine signifikante Verbesserung des Korrosionsverhaltens der generierten Schichten im Vergleich zum Ausgangszustand nachgewiesen werden. EB-umschmelzlegierte Schichten weisen im Ergebnis von Trockenverschleißtests (Stift-Scheibe) eine deutliche Reduzierung des spezifischen Verschleißkoeffizienten auf.

Ce sujet entre dans le cadre de l'étude d'un procédé d'oxydation avancé innovant dans le domaine de la dépollution des eaux, à savoir l'ionisation par faisceau d'électrons. Le radical hydroxyle (•OH) et l'électron hydraté (e−aq) sont les deux espèces majoritaires issues de l'ionisation de solutions aqueuses par un faisceau d'électrons d'intense énergie. Il a été démontré que la génération des radicaux supplémentaires tels que le radical sulfate (SO4•−) et le radical hydroxyle par les réactions radicalaires entre l'ion persulfate, le peroxyde d'hydrogène et l'électron hydraté respectivement, améliore l'efficacité de ce procédé pour la dégradation de polluants organiques en solution aqueuse. Dans le présent travail, la dégradation et la minéralisation de benzènesulfonate et naphthalènesulfonate de sodium, et d'acide gallique ont été obtenues par irradiation par faisceau d'électrons seul et couplé avec un oxydant (S2O8−−, H2O2). En absence d'oxydant une dose absorbée de 1,5 kGy a été suffisante pour l'élimination totale de ces composés. La présence d'oxydant permet généralement de réduire les doses d'irradiation nécessaires. Par ailleurs, l'augmentation de la concentration en oxydant ou de la dose appliquée a un effet bénéfique vis-à-vis de l'élimination du carbone organique. Cependant, le couplage S2O8−−/faisceau d'électrons est plus adapté que le couplage H2O2/faisceau d'électrons même en présence de constituants inorganiques. Les résultats obtenus soulignent l'importance du rôle du dioxygène dissous lors de l'étape de la minéralisation en vue de favoriser la formation des radicaux organiques (ROO•). Pour chaque une des molécules étudiées, des sous-produits d'oxydation... / This research belongs to the study of the ionization of aqueous solutions by electron beam (E.B.) as an advanced oxidation process for water treatment. The hydroxyl radical (•OH) and hydrated electron(eaq¯) are the two major active species produced from the ionization of aqueous solutions by high energy electron beam. It has been shown that the generation of additional radicals such as the sulphate radical (SO4•¯) and hydroxyl radical from the reaction of persulfate ion (S2O8¯) or hydrogen peroxide (H2O2) with the hydrated electron, improved the efficiency of this process towards the degradation and mineralization of organic pollutants in aquaeous solution. In the présent work, the degradation and mineralization of naphthalenesulfonate, benzenesulfonate and gallic acid were studied by electron beam irradiation alone and coupled with oxidants (S2O8¯, H2O2).In the absence of oxidant, an absorbed dose of 1,5 kGy leads to total elimnation of these pollutants. The presence of added oxidants usually reduces the radiation dose required. In addition, increasing oxidant concentration or applied dose had a beneficial effect towards the organic carbon removal. It was found that coupling E.B./S2O8¯ has more suitable than E.B./ H2O2 even in the presence of inorganic constituents. The results also highlighted the importance of dissolved oxygen in the system when mineralization is aimed. For each of the molecules studied, oxidation by-products resulting from hydroxylation and aromatic ring opening were identified.

This thesis studies a scheme to fabricate small-scaled metal structures by electrochemical metal deposition and lift off. The key point is the use of self-assembled monolayers (SAMs) to control both interfacial charge transfer in electrodeposition and adhesion of the deposit to the substrate. Patterned SAMs exhibiting blocking and non-blocking areas are applied as templates in electrochemical deposition of Cu or Au. Thiol SAMs on Au substrates are used, namely alkane thiols and thiols combining an aliphatic chain with a biphenyl or biphenyl analogous pyridine-phenyl moieties. The patterning of SAMs is realised with microcontact printing (μCP) and electron beam lithography. Electrochemical deposition based on defects in the SAMs is optimised towards generating small nanostructures and depending on the system single or stepped potential procedures are applied. Generated metal structures are transferred to an insulator by lift off. Au microstructures (~10 μm) have been made with microcontact printing and transferred onto epoxy glue, which can potentially be used as microelectrodes in electroanalytical chemistry. Sub-100 nm Cu features and sub-40 nm Au features have been created with electron beam lithography respectively. Lift off process has successfully transferred Cu nanostructures onto epoxy glue with high precision. In contrast to the deposition mediated by defects, Cu deposition mediated by discharging Pd²⁺ coordinated to a pyridine terminated SAM directly through the SAM molecules has been explored as a new approach. This new approach has potential to decrease the size of the metal structure further and the preliminary results show possibility of sub-10 nm features. SAMs prepared with a newly synthesised molecule, 3-(4'-(methylthio)-[1,1'-biphenyl]-4-yl)propane-1-thiol, are characterised by STM, XPS and NEXAFS. The metal structures are investigated by SEM, AFM and STM.

La présente étude est dédiée à la compréhension des mécanismes de malaxage intervenant lors du soudage de matériaux dissimilaires par des sources de haute énergie et en particulier sur deux couples de matériaux présentant des problèmes métallurgiques différents : • cuivre - inox (lacune de miscibilité, différence de propriétés thermophysiques),• TA6V- inox (oxydation, formation de phases intermétalliques fragilisant la soudure).Pour le premier couple de matériaux, le soudage par laser Nd:YAG continu et par faisceau d'électrons a été utilisé. L'étude des évolutions de la morphologie des soudures, de la composition et de la microstructure des zones fondues ainsi que des propriétés mécaniques a permis de proposer des hypothèses sur les mécanismes de formation du mélange hétérogène à solubilité limitée. Afin de quantifier les phénomènes physiques intervenant en soudage continu de matériaux dissimilaires, la modélisation numérique a été mise en œuvre en utilisant le logiciel FEM "Comsol Multiphysics". Une série des modèles simulant les champs de températures, les mouvements convectifs et le malaxage (diffusion, méthode level set, méthode des champs de phases) a été créée. Dans le cas du laser, la formulation pseudo-stationnaire du transfert de chaleur basée sur la géométrie du capillaire simplifiée et la convection a été couplée avec les problèmes 2D de diffusion et de malaxage des matériaux dans différents plans horizontaux. En soudage par faisceau d'électrons, la morphologie de la microstructure a nécessité une formulation temporelle. Le modèle multiphysique final en couplage complet (solution multiphysique simultanée) reproduit le processus de formation d'une structure périodique de solidification lors du soudage par faisceau d'électrons et permet d'expliquer l'aspect des structures alternées entre matériaux immiscibles ou présentant de grandes différences de propriétés thermophysiques.Le deuxième couple de matériaux présente des problèmes métallurgiques majeurs liés à la formation des phases intermétalliques rendant l'assemblage direct par fusion impossible. La composition locale devient donc l'aspect-clef de la formation d’une soudure correcte : l'introduction d’un troisième matériau (cuivre) ayant une meilleure compatibilité avec le titane est nécessaire. Pour pouvoir déterminer les fenêtres optimales des conditions opératoires, les modèles numériques, créés précédemment, ont été adaptés pour quatre procédés de l’assemblage : faisceau d'électrons, soudage lasers Nd:YAG continu et pulsé, brasage par laser avec apport de fil. L'analyse élémentaire des microstructures dans les soudures résistantes mécaniquement a permis de développer le scénario de la solidification d'une zone fondue et de comprendre l'influence de la composition aux interfaces sur la résistance mécanique des assemblages.Les modèles numériques multiphysiques créés au cours de cette étude permettent l'accès rapide à la grande quantité d'information sur le comportement de la zone fondue en fonction des paramètres de soudage en se basant sur le nombre des données de départ relativement limité et sur quelques hypothèses simplificatrices. L'approche multiphysique à la modélisation de soudage permet de reproduire la forme de la zone fondue, visualiser les écoulements du liquide et cartographier la distribution de certains éléments avec une bonne corrélation avec les résultats expérimentaux. L'ensemble des modèles permet de déterminer les conditions opératoires répondant aux critères fixes en fonction de la métallurgie d'un couple hétérogène. / The present study is dedicated to the comprehension of the mechanism of materials mixing during dissimilar welding by high power beam sources. We have been interested in joining of two couples of metallic materials which present different metallurgical problems: • copper- stainless steel (miscibility gap, important difference in physical properties);• TA6V- stainless steel (oxidation on air, formation of intermetallic phases which made the joint brittle).For the first couple of materials, continuous laser Nd:YAG welding and electron beam welding have been applied. The experimental study of morphology evolution, composition, microstructure and mechanical properties has allowed establishing the hypotheses on formation of heterogeneous mixture between the materials having limited solubility. To quantify the physical phenomena of continuous dissimilar welding, the numerical modeling has been carried out by means of FEM software package "Comsol Multiphysics". A number of models reproducing temperature field, convection movements and mixing (diffusion, level set method, phase field method) between the materials has been created. In case of continuous laser welding, the pseudo-stationary formulation of heat transfer based on simplified key-hole geometry and convection has been coupled with two-dimensional problems of diffusion and mixing in horizontal planes. The electron beam welding presenting the nonlinear development of the weld has needed employing of temporary formulation. Final model including complete coupling (simultaneous multiphysical solving) reproduces the process of development of periodic solidification structure during electron beam welding and allows explaining the mechanism of formation of altered structures between immiscible materials which have important difference in thermophysical properties.The second couple of materials presents weldability problems due to formation of brittle intermetallic phases making direct joining by fusion impossible. The local elementary composition becomes the key-aspect of successful joining: the introduction of the third material (pure copper) having better compatibility with titanium is necessary. To determine the ranges of optimal operational conditions, numerical models created previously have been adapted to the case of four joining techniques: electron beam and laser Nd:YAG (continuous and pulsed) welding and laser brazing with filler wire. Elementary analysis of microstructures of resistant welds has allowed developing the solidification scenario and understanding the influence of local composition of heterogeneous interfaces on tensile properties of the joints. The multiphysical models created during this study allow rapid access to high quantity of data on behavior of melted zone in function of welding parameters basing on relatively limited input data and several simplification hypotheses. The multiphysical approach to welding modeling allows recreating the shape of melted zone, to visualization the convection movements and providing the cartography of several elements in good correspondence with experimental results. A set of models allows determination of operational parameters respecting fixed criterions determined by metallurgy of dissimilar couple.

The thesis focuses on exploring the sub-grain structure in stainless steel 316L prepared by additive manufacturing (AM). Two powder-bed based AM methods are involved: selective laser melting (SLM) and electron beam melting (EBM). It is already known that AM 316L has heterogeneous property and hierarchy structure: micro-sized melt pools, micro-sized grains, nano-sized sub-grain structure and nano-sized inclusions. Yet, the relation among these structures and their influence on mechanical properties have not been clearly revealed so far. Melt pool boundaries having lower amount of sub-grain segregated network structures (Cellular structure) are weaker compared to the base material. Compared with cell boundaries, grain boundaries have less influence on strength but are still important for ductility. Cell boundaries strengthen the material without losing ductility as revealed by mechanical tests. Cellular structure can be continuous across the melt pool boundaries, low angle sub-grain boundaries, but not grain boundaries. Based on the above understanding, AM process parameters were adjusted to achieve customized mechanical properties. Comprehensive characterization were carried out to investigate the density, composition, microstructure, phase, magnetic permeability, tensile property, Charpy impact property, and fatigue property of both SLM and EBM SS316L at room temperature and at elevated temperatures (250°C and 400°C). In general, SLM SS316L has better strength while EBM SS316L has better ductility due to the different process conditions. Improved cell connection between melt pools were achieved by rotating 45° scanning direction between each layer compared to rotating 90°. Superior mechanical properties (yield strength 552 MPa and elongation 83%) were achieved in SLM SS316L fabricated with 20 µm layer thickness and tested in the building direction. Y2O3 added oxide dispersed strengthening steel (ODSS) were also prepared by SLM to further improve its performance at elevated temperatures. Slightly improved strength and ductility (yield strength 574 MPa and elongation 90%) were obtained on 0.3%Y2O3-ODSS with evenly dispersed nanoparticles (20 nm). The strength drops slightly  but ductility drops dramatically at elevated temperatures. Fractographic analysis results revealed that the coalescence of nano-voids is hindered at room temperature but not at elevated temperatures. The achieved promising properties in large AM specimens assure its potential application in nuclear fusion. For the first time, ITER first wall panel parts with complex inner pipe structure were successfully fabricated by both SLM and EBM which gives great confidence to application of AM in nuclear industry. / <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 4: Manuscript. Paper 5: Manuscript.</p>

Le présent travail de thèse a été effectué dans le cadre du projet CPER-FEDER MATISSE, projet coordonné par l’UTT regroupant deux autres partenaires : Nanovation et l’URCA. Le projet avait pour ambition la croissance des couches minces de ZnO de haute qualité et leur valorisation.Le ZnO cristallin est un semiconducteur à grand gap avec d’excellentes propriétés optiques. Son énergie de liaison excitonique de 60meV est l’une des caractéristiques qui lui valent tant d’attention malgré sa difficile gravure physique qui hypothèque la réalisation de composants photoniques compacts. En effet, la longueur d’onde d’émission du ZnO est de l’ordre de 375nm, impliquant l’utilisation de structures de petite taille dont la réalisation relève des nanotechnologies.Trois objectifs scientifiques ont été poursuivis : l’amélioration de l’extraction de l’émission excitonique dans les couches minces de ZnO par ingénierie de gap en utilisant les cristaux photoniques, l’émission laser et son contrôle et enfin, le transfert d’énergie du ZnO vers les QDots comme couche de phosphores pour la conversion de l’émission UV en lumière blanche. Pour y parvenir, deux technologies ont été utilisées : la croissance PLD (Nanovation) et la structuration par approche top-down délaissée par la communauté scientifique.La thèse traite de la structuration par lithographie électronique combinée à la gravure RIE-ICP et les études scientifiques associées. Les résultats obtenus sont concluants avec parfois des records comme pour le gain (>1000cm-1) et les pertes optiques (<10cm-1). Nous avons également procédé à la réalisation des premiers composants optoélectroniques : laser MIS et photodétecteur MSM / This work was conducted in the framework of the MATISSE project supported by the CPER-FEDER. Coordinated by UTT and including two other partners: Nanovation and URCA, the main project objective was the growth of high quality ZnO thin films and their valorization.ZnO is a wide band gap semiconductor with excellent optical properties. Its exciton binding energy (60meV) is one of the most important characteristics that earned to ZnO more attention despite its physical etching which is difficult to perform. Indeed, the excitonic emission of ZnO occurs approximately at 375nm, which involves the use of small structures whose achievement leads to the use of nanotechnology.Three scientific objectives were pursued: improving the extraction of the excitonic emission in ZnO thin films by engineering the photonic band gap by using photonic crystals, laser emission and control and finally, energy transfer from ZnO to QDots used as phosphors for down conversion of the UV emission to white emission. To achieve this, two technologies were used: PLD growth (Nanovation) and top-down structuring approach neglected by the scientific community.The thesis mainly deals with the structuring by electron beam lithography combined with ICP - RIE and related scientific studies. Conclusive results have been obtained such as high optical gain (>1000 cm-1) and low optical losses (<10 cm-1). We also carried out first optoelectronic components: MIS laser and MSM photodetector

The titanium alloy, Ti-6Al-4V, is vastly studied and used in many applications because it has a transformation microstructure, which can be tailored for apt properties that are consistent up to 500°C. Compared to conventional steels, this alloy favours certain applications due to its high specific strength, hardenability, corrosion resistance, biocompatibility and weldability. Its weldability makes the alloy a good candidate for additive manufacturing (AM). Ti-6Al-4V parts are widely built by the AM process of electron beam melting (EBM). However, heat transfer remains crucial in EBM process. The high intensity localized, moving, electron beam heat source and the rapid self-cooling are critical, especially in thin parts/ sections. When thin sections are built by the EBM process, there will be microstructural variation in their build direction, which can lead to the variation of their mechanical properties. It is necessary to understand the microstructure and mechanical properties of thin sections when they are used as functional parts in various applications in aerospace, automotive, medical, etc. industries. The microstructure, tribological behaviour and mechanical properties of Ti-6Al-4V, as-built EBM thin plates were studied by means of various hardness, scratch and tensile testing. The hardness and scratch tests were performed on the thin plates to correlate the microstructural variation. In-situ micro tensile test was performed inside the scanning electron microscope (SEM), to see the sample’s deformation behaviour. Microstructural characterization revealed equiaxed grains in the transverse section and the longitudinal surface exhibited columnar grains elongated along the build direction. The size of the equiaxed grains are found to vary across the thickness of the plate. The indentation and scratch hardness also vary in correlation with the varying grain size across the plate’s thickness. The micro tensile results reveal that the tensile properties of the thin plate are comparable to that of its bulk Ti-6Al-4V counterpart.

Titanium and aluminium alloys are among the most used construct materials due to their physical and mechanical properties except steels. The joining of these alloys can improve properties of whole construction but it is still difficult task. Especially welding of titanium and aluminium alloys is difficult cause formation of undesirable intermetalic phases in the weld. This thesis focuses on influences of electron beam welding parameters especially focusing and deflection of beam and preheating of base material to quality of heterogeneous join of titanium alloy Ti6Al4V and aluminium alloy EN AW-6061 – T651. There is described preparation of welded joins and brazed joins in the thesis, which are evaluated by light microscopy, scanning electron microscopy and EDS analysis of chemical composition. There was evaluated presence and chemical composition of formated intermetalic phases in the welded joins and quality and defects in the brazed joins.