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Cette thèse porte sur l’amélioration de la résistance au flux laser de la surface descomposants optiques en silice en régime nanoseconde. Ce matériau est utilisé sur lesinstallations de laser de puissance telles que le Laser Mégajoule. Pour augmenter la durée de viedes composants optiques et garantir le fonctionnement nominal de cette installation,l’endommagement laser doit être maîtrisé. Il s’agit d’une dégradation irréversible de la surfacedes composants causée par l’interaction entre le faisceau laser et des défauts précurseurs. Cesderniers sont une conséquence de la synthèse de la silice puis du polissage des composants etleur présence peut être limitée par une action de traitement chimique réalisée à l’issue dupolissage qui consiste à éroder la surface de silice à l’aide d’une solution chimique. Cette érosionne doit cependant pas dégrader la qualité de la surface polie et ses propriétés optiques. Cettethèse se concentre sur la réalisation de cette étape de traitement chimique et se décompose entrois études. La première porte sur la caractérisation de la pollution induite en surface par lepolissage et sa suppression par le traitement chimique. La seconde et la troisième analysentl’impact des traitements chimiques respectivement sur les propriétés optiques de la surface etsur les rayures de polissage. Ces études nous permettent d’évaluer l’influence des différentsparamètres du traitement chimique, tels que la solution, le système de mise en oeuvre etl’épaisseur érodée, sur les performances apportées aux composants optiques. Finalement,l’ensemble de ces connaissances nous conduit à proposer un traitement chimique optimisé quiaméliore la tenue au flux des composants optiques sans dégrader leurs propriétés optiques. / In this thesis, laser-induced damage resistance improvement of fused silica opticsis investigated in the nanosecond regime. This material is used on high power laser facilitiessuch as the Laser Mégajoule. In order to improve the optics life time and to ensure the nominaloperation of this facility, laser induced damage has to be controlled. This phenomenon is anirreversible modification of the components surface because of the interaction between the laserbeam and precursors defects. These defects are a consequence of the synthesis of silica and thepolishing of the optics and their presence can be reduced by a wet etching. This process consistsin an erosion of the surface using a chemical solution however optical properties must remainunchanged. In this thesis, we focus on the wet etching process and we conduct three studies. Thefirst one is about the characterization of the polishing induced contamination and the capabilityof a wet etching to remove it from the surface. The second and the third analyzes are about theimpact of the wet etching respectively on the surface and on the scratches. These studies allowus to evaluate the influence of the wet etching parameters as the chemical solution, the systemused and the deep etched. Finally, the highlights obtained thanks to these studies enable tooptimize the wet etching process and improve the laser induced damage resistance ofcomponents without compromising their optical properties.

Additive manufacturing is gaining popularity at a rapid rate and has been a resourceful production process to reduce material usage, wastage (scrap) and manufacturing costs for various applications. The project conducted, emphasizes on Thermoplastic Elastomer (TPE SE6300C-65A) material, which is a highly versatile compound, and has the ability to exhibit properties of both rubber (Elastomers) in terms of flexibility and plastic (Polymers) in terms of recyclability. Cost reduction without compromising quality is one of the important factors for industries. The project involves the use of TPE pellets to extrude filaments that could be used for 3D Printing. Filament extrusion involves process variables like Nozzle Temperature, De-humidification of pellets, Diameter of the nozzle, Distance of collection, Cooling and Angle of inclination of the extruder. These process variables are optimized to accomplish the desired quality of filament. The filament produced through extrusion is further used to make products using Fused Deposition Modeling (FDM). FDM also involves numerous process variables like Layer Thickness, Build Orientation, Print Infill, Print Speed etc. In this study, different test specimens, in terms of geometrical shapes are printed from the material, TPE SE6300C-65A and tested in order to understand how the surface features as well as the dimensional accuracy change with different process variables. It is observed that the surface topography produced throughout FDM process is majorly affected by the angle of orientation of the printed part. The main goal of this thesis is to give the reader a better understanding on which process variable, such as layer thickness, temperature and print speed affect the surface roughness of the models and also a comparison between these three variables, highlighting which is more or less affecting. It is also observed the dimensional accuracy of the real specimen deviate from the value input into the CAD software. The results obtained in this study clearly suggest that there is a lot of opportunities for future improvements especially regarding the dimensional accuracy, it is imperative to achieve the highest precision possible in order to have commercial values for the FDM 3D printing.

O estudo comparativo da distribuição de tensões de von Mises em dente endodonticamente tratado, com dois formatos de retentores intra-radiculares, pré-fabricado cilíndrico/escalonado e fundido cônico, foi realizado pelo método dos elementos finitos em modelos tridimensionais de caninos superiores com geometria axi-simétrica e restaurados com coroas metalocerâmicas, aplicando-se uma carga oblíqua de 100N com 45 º de inclinação em relação ao seu longo eixo. Os resultados indicaram uma discreta diferença nos dois modelos (formatos) de retentores. O pino escalonado neutralizou mais as cargas no sentido corono-apical e no pino cônico ficou evidenciado o efeito de cunha. / The aim of this study was to compare the von Mises stress distribution on a human canine teeth endodontically treated and restored with two types of post and core. The analysis was made using the three dimensional Finite Element Analysis method. For the analysis was created and axy-simetric structure of the teeth, including a porcelain fused to metal crown, a cement layer, and the periodontal structures. The model was analyzed when a 100N load was applied on the surface of the crown with 45º angulation with the long axis of the teeth. The results showed that both models exhibit little difference, the “stair shape” post system neutralized the axial loads, and the conical shape post showed a wedge effect on the apical third of the root.

The ease of manufacturing complex geometries using fused deposition modeling (FDM) 3D-Printing reduces the overall production cost compared with the traditional manufacturing techniques. Because of the benefits of 3D printing technologies, it is proposed to be used in the manufacturing of different products. But there is still no definite characterization of the surface quality of objects manufactured by 3D printing. Hence in order to define the texture of the surfaces produced, measurements from different samples are taken and quantified.In this study, a 3D test model consisting of various slopes is printed at different layer thicknesses and different print speeds using different 3D printers.Thus, the effect of the surface orientation on the surface roughness was studied in relation to the different layer thicknesses and different print speeds. The study samples are measured using the state of the art equipment at Halmstad University.This thesis studies the surface roughness at different slopes of FDM models.A related study on the dimensional variation between the CAD model and the actual3D printed model, and causes/reasons for the variations are analyzed.It is observed that FDM produced part surface topography is directly affected by the orientation of the surface. Also, the surface roughness increases with increase in layer thickness. The observed correlations between surface roughness and layer thickness and surface orientation could be used to better understand the behavior of FDM surfaces, thus to better quantify the surface roughness. To improve quality, it must first be quantified. It is well observed that dimensional inaccuracy exists between the CAD model and the printed part. These results suggest that there is a lot of work and improvements to be done in order to close the gap of dimensional inaccuracy and achieve a high precision commercial FDM 3Dprinting.

Digital RF phase shifters fabricated using additive manufacturing processes are presented and studied. The purpose is to explain the performance differences between phase shifters fabricated using additive manufacturing and those fabricated with conventional subtractive techniques. All phase shifters are designed to operate at a center frequency of 2.45 GHz with a 100 MHz bandwidth. The 1-bit 45° switched line phase shifters have an average insertion loss of 1.3 dB and a 220 mm2 footprint, while the 1-bit 180° high-pass low-pass phase shifters have an insertion loss 1.56 dB and a 180 mm2 footprint. The 4-bit high-pass low-pass, switched line hybrid phase shifters on the other hand show an average state insertion loss of 5.4 dB and have a 660 mm2 foot print. By carefully analyzing the performance of the various phase shifter designs it is shown that the limiting factors of additive manufacturing technology are the low conductivity of CB028 silver ink in comparison to copper, and the inability to print dielectrics with low surface roughness. Finally, parallel plate capacitors and a spiral inductor designed to be fabricated using additive manufacturing techniques are studied. This is done in order to better understand the advantages and disadvantages of such a design. By analyzing the component’s simulated performance it is shown that 3D printed capacitors and inductors are feasible as long as the capacitance or inductance values needed are low. Large value 3D printed components are impractical for RF applications due to their large size.

This thesis aims to investigate the use of additive manufacturing (AM) as a novel manufacturing process for the production of milli-scale chemical reaction systems. Five well developed additive manufacturing techniques; stereolithography (SL), selective laser melting (SLM), fused deposition modelling (FDM), ultrasonic additive manufacture (UAM) and selective laser sintering (SLS) were used to manufacture a number of miniaturised flow devices which were tested using a range of organic and inorganic reactions. SL was used to manufacture a range of functioning milli-scale flow devices from Accura 60 photoresin, with both simple and complex internal channel networks. These devices were used to perform a range of organic and inorganic reactions, including aldehyde and ketone functional group interconversions. Conversion of products within these reactors, were shown to be comparable to commercially available milli-scale coil reactors. More complex designs, which allowed SL parts to be integrated to existing flow and analytical instrumentation, allowed us to develop an automated reaction analysis and optimisation platform. This platform allowed precise control over the reaction conditions, including flow rate, temperature and reagent composition. We also designed a simplex type reaction optimisation software package that could input data in the form of reaction conversions, peak intensities, and thermocouple data, and generate a new set of optimal reaction conditions. SL parts which incorporated embedded analytical components were also manufactured, which allowed us to perform inline reaction analysis as a feedback method for input into the optimisation platform. Stereolithography was shown to be a highly versatile manufacturing method for designing and producing these flow devices, however the process was shown to be still limited by the range of processable materials currently commercially available. SLM was also used to manufacture a number of functioning milli-scale flow devices from stainless steel and titanium, which had simplistic internal channel designs of diameters ranging from 1 to 3 mm. Again, SLM parts were manufactured which incorporated embedded analytical components, which could be integrated into an automated reaction platform. These devices, unlike parts produced via SL, could be attached to heating platforms to allow us to perform high temperature reactions. This control over the reaction temperature formed an essential part of the reaction optimisation platform. These parts were again used to perform a ketone functional group interconversion. Internal structures of these SLM parts were also visualised via micro computed tomography (μCT or microCT) scanning as well as optical microscopy. FDM was used throughout the project as an inexpensive method of prototyping parts which were to be manufactured via more expensive manufacturing processes. This prototyping allowed the optimisation of intricate design features, such as the manufacture of an inline spectroscopic flow cell for integration with a commercially available LC system. FDM was also proposed as a customisable approach to designing and manufacturing flow devices with embedded components, however the current limitations in build resolution and materials choices severely limited the use of FDM for this application. UAM was also proposed as a novel manufacturing process whereby the build process would allow discrete components to be embedded directly into a flow channel. This was demonstrated by embedding a type-k thermocouple across a 2 mm channel. The data from this thermocouple was monitored during a heated reaction, and used as a method of determining the exact reaction conditions the reaction medium was being exposed to. SLS was also proposed as a possible manufacturing method for milli-scale flow devices, however it proved difficult to remove un-sintered powder from parts with internal channel diameters as high as 5 mm. It was shown that this powder was forming a dense semi solid, due to the large degree of shrinkage upon cooling of the SLS parts, which was compressing the powder. More research into optimum processing conditions is required before SLS could be used for the production of intricate channel networks.

Lors de ces trois années de thèse, le développement de nouvelles molécules luminescentes, reposant sur la stabilisation d’un squelette dibenzoBODIPY a été réalisé. Dans un premier temps, la modulation des propriétés photophysiques a été effectuée (par introduction de groupement aromatique et/ou donneur soit lors de la formation du dibenzoBODIPY, soit par couplage croisé). Dans un second temps, nous nous sommes intéressés à la synthèse de dibenzoBODIPYs dissymétriques. La dissymétrie des composés a été réalisée soit par condensation mixte de dicétone soit par mono-couplage des dibenzoBODIPYs. L’utilisation de ces derniers a permis d’obtenir des dibenzoBODIPYs chiraux (soit par formation de liaison C-B, soit par formation de liaison B-O). La mono-fonctionnalisation intramoléculaire par le groupement phénol formé in situ est la première à ce jour. Enfin la formation de nouveau BODIPYs β-fusionnés par un hétérocycle a été entrepris. Nous avons synthétisé le premier BODIPY β-fusionné par un benzofurane. / During this PhD, the development of new luminescent molecules based on the stabilization of a dibenzoBODIPY scaffold was performed. Firstly, the modulation of the photophysical properties was carried out by the introduction of an aromatic and/or a donor group, either during the formation of dibenzoBODIPY or by cross-coupling. Secondly, we were interested in the synthesis of asymmetrical dibenzoBODIPYs. The dissymmetry of compounds was done either by mixed condensation of a diketone or by dibenzoBODIPYs mono-coupling. The use of the latters yielded chiral dibenzoBODIPYs either by C-B bond formation, or by B-O bond formation. Intramolecular mono-functionalization phenol formed in situ has never been reported so far. Finally, the synthesis of β‑fused BODIPYs with a heterocycle was undertaken. We synthesized the first β‑fused BODIPYs by a benzofuran

This thesis presents a multiscale investigation and characterization of additive manufactured Polyamide material using fused deposition modelling technique. Manufacturing was performed using Markforgeds – Mark one 3D printer.  A multiscale investigation dedicated to minimizing the effect of shape distortion during 3D printing are presented, focusing on both molecular alignment in microstructure and implementing internal structures in mesostructure. Characterization on samples investigating microstructure was performed with coefficient of linear thermal expansion measurement and 3-point bending experiment. Different samples with varying infill patterns are tested and results indicates an isotropic behaviour through the manufactured samples and implies no molecular alignment due to printing pattern. In meso-structure, an implemented internal pattern is investigated. All samples are measured with 3D scanning equipment to localize and measure the magnitude of shape distortion. Attempts to find relationships in shape distortion and porosity between the samples resulted in no observed trends. Compressive experiments where performed on samples in axial- and transverse directions resulting in anisotropic behaviour. The largest compressive stiffness is recorded in axial direction reaching 0,33 GPa. The study is done in collaboration with Swerea SICOMP and Luleå University of Technology.

A general and modular synthetic approach to 4-substituted phenyl, 2-substituted pyridin- 5-yl and 5-substituted pyridin-2-yl 2′-C-methyl-C-ribonucleosides as potential anti-HCV agents was developed. Addition of halo(het)aryllithium reagents to benzylated 2-C-methyl-D- ribonolactone gave the corresponding hemiketals, which were subsequently converted to the β-anomeric benzyl-protected bromo(het)aryl-C-nucleosides via either direct reduction (in the case of phenyl derivative) or acetylation followed by reduction of the resulting hemiketal acetates (in the case of pyridyl derivatives). The key halogenated (het)aryl-C-nucleoside intermediates were further transformed by Pd-catalyzed cross-coupling, hydroxylation and amination reactions affording series of protected C-nucleosides with small hydrophilic and hydrophobic substituents. The final protecting group removal was rather problematic, and different debenzylation methods, such as hydrogenation on Pd/C or treatment with BCl3, had to be optimized for each derivative to minimize the formation of side-products. The final C- nucleosides were also converted into their 5′-O-triphosphates, and biological activity screenings revealed that none of the free C-nucleosides possesses any antiviral activity in the HCV replicon assay, and none of their NTPs...