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<p> Optical metamaterials have triggered extensive studies driven by their fascinating electromagnetic properties that are not observed in natural materials. Aside from the extraordinary progress, challenges remain in scalable processing and material performance which limit the adoption of metamaterial towards practical applications. The goal of this dissertation is to design and fabricate nanocomposite thin films by combining nitrides with a tunable secondary phase to realize controllable multi-functionalities towards potential device applications. Transition metal nitrides are selected for this study due to the inherit material durability and low-loss plasmonic properties that offer stable two-phase hybridization for potential high temperature optical applications. Using a pulsed laser deposition technique, the nitride-metal nanocomposites are self-assembled into various geometries including pillar-in-matrix, embedded nanoinclusions or complex multilayers, that possess large surface coverage, high epitaxial quality, and sharp phase boundary. The nanostructures can be further engineered upon precise control of growth parameters. </p><p> This dissertation is composed of a general review of related background and experimental approaches, followed by four chapters of detailed research chapters. The first two research chapters involve hybrid metal (Au, Ag) - titanium nitride (TiN) nanocomposite thin films where the metal phase is self-assembled into sub-20 nm nanopillars and further tailored in terms of packing density and tilting angles. The tuning of plasmonic resonance and dielectric constant have been achieved by changing the concentration of Au nanopillars, or the tuning of optical anisotropy and angular selectivity by changing the tilting angle of Ag nanopillars. Towards applications, the protruded Au nanopillars are demonstrated to be highly functional for chemical bonding detection or surface enhanced sensing, whereas the embedded Ag nanopillars exhibit enhanced thermal and mechanical stabilities that are promising for high temperature plasmonic applications. In the last two chapters, dissimilar materials candidates beyond plasmonics have been incorporated to extend the electromagnetic properties, include coupling metal nanoinclusions into a wide bandgap semiconducting aluminum nitride matrix, as well as inserting a dielectric spacer between the hybrid plasmonic claddings for geometrical tuning and electric field enhancement. As a summary, these studies present approaches in addressing material and fabrication challenges in the field of plasmonic metamaterials from fundamental materials perspective. As demonstrated in the following chapters, these hybrid plasmonic nanocomposites provide multiple advantages towards tunable optical or biomedical sensing, high temperature plasmonics, controllable metadevices or nanophotonic chips.</p><div><br></div>

Beschäftigte im öffentlichen Dienst sind einer steigenden Zahl von Übergriffen und Bedrohungen ausgesetzt. Auch in den Statistiken der Unfallversicherungsträger und der Polizei findet sich das Phänomen Gewalt verstärkt wieder. Die Wahrscheinlichkeit einer Verletzung durch eine Stichwaffe ist in Deutschland deutlich höher einzustufen als die mittels einer Schusswaffe bzw. einem Projektil. Zudem werden stichhemmende und Stichschutzwesten nicht nur für den Einsatz im behördlichen, militärischen und Sicherheitsbereich angeboten, sondern auch für Privat- und Geschäftsleute. Die Westen sollen die Träger vor Angriffen mit Messern, Nadeln und spitzen Gegenständen schützen, sind jedoch in ihrem Tragekomfort verbesserungswürdig. Derzeit erfolgt die Abschwächung von Angriffen mit Stichwaffen durch integrierte Schutzplatten aus Aluminium, Edelstahl, Kunststoff, Keramik und/oder Metall-Ringgeweben. Die Stichschutzwesten besitzen zum einen ein beträchtliches Gewicht (je nach Modell und Größe 1,5 bis 5 kg). Zum anderen weisen sie bei langer Tragedauer und hohen Außentemperaturen (z. B. während der Sommermonate) ein schlechtes thermophysiologisches Verhalten auf. Üblicherweise nimmt die Schutzwirkung mit steigendem Gewicht zu. Eine Gewichtserhöhung vermindert jedoch den Tragekomfort, wodurch auch die Trageakzeptanz, d. h. die Bereitschaft einer Person zum Tragen der Schutzkleidung, verringert wird. Diese Trageakzeptanz stellt ein entscheidendes Kriterium für den erfolgreichen Personenschutz dar. Einen möglichen Lösungsansatz bietet die Realisierung von Leichtbaupotenzialen mittels neuer Technologien und hybriden Materialien. Durch eine Überarbeitung des bisherigen Designs der Schutzkleidung soll der Tragekomfort unter Beibehaltung der Funktionalität deutlich verbessert werden. Statt der bisher angewandten Schutzplatten wird eine körperformabhängige Segmentierung von bioinspirierten Interlocking-Strukturen aus Hochleistungsfaserstoffen entwickelt. Die Verstärkungskomponente mit hoher Schlagzähigkeit, Bruchdehnung und Zugfestigkeit besteht aus Aramidfasern. Zudem werden die Stichschutzelemente mittels additiver Fertigung auf biegeweiche Maschenwaren appliziert. Die Schutzkleidung lässt sich an die jeweilige Körperform anpassen und bietet neben dem Stichschutz einen verbesserten ergonomischen, thermophysiologischen sowie hautsensorischen Komfort. [... aus der Einleitung]

<p>Nonlinear transmission lines (NLTLs) provide a solid state alternative to conventional vacuum based high power microwave (HPM) sources. The three most common NLTL implementations are the lumped element, split ring resonator (SRR), and the nonlinear bulk material based NLTLs. The nonlinear bulk material implementation provides the highest power output of the three configurations, though they are limited to pulse voltages less than 50 kV; higher voltages are possible when an additional insulator is used, typically SF₆ or dielectric oil, between the nonlinear material and the outer conductor. The additional insulator poses a risk of leaking if structural integrity of the outer conductor is compromised. The desire to provide a fieldable NLTL based HPM system makes the possibility of a leak problematic. The work reported here develops a composite based NLTL system that can withstand voltages higher than 50 kV and not pose a risk of catastrophic failure due to a leak while also decreasing the size and weight of the device and increasing the output power.</p> <p>Composites with barium strontium titanate (BST) or nickel zinc ferrite (NZF) spherical inclusions mixed in a silicone matrix were manufactured at volume fractions ranging from 5% to 25%. The dielectric and magnetic parameters were measured from 1-4 GHz using a coaxial airline. The relative permittivity increased from 2.74±0.01 for the polydimethylsiloxane (PDMS) host material to 7.45±0.33 after combining PDMS with a 25% volume fraction of BST inclusions. The relative permittivity of BST and NZF composites was relatively constant across all measured frequencies. The relative permeability of the composites increased from 1.001±0.001 for PDMS to 1.43±0.04 for a 25% NZF composite at 1 GHz. The relative permeability of the 25% NZF composite decreased from 1.43±0.05 at 1 GHz to 1.17±0.01 at 4 GHz. The NZF samples also exhibited low dielectric and magnetic loss tangents from 0.005±0.01 to 0.091±0.015 and 0.037±0.001 to 0.20±0.038, respectively, for all volume fractions, although the dielectric loss tangent did increase with volume fraction. For BST composites, all volume fraction changes of at least 5% yielded statistically significant changes in permittivity; no changes in BST volume fraction yielded statistically significant changes in permeability. For NZF composites, the change in permittivity was statistically significant when the volume fraction varied by more than 5% and the change in permeability was statistically significant for variations in volume fraction greater than 10%. The DC electrical breakdown strength of NZF composites decreased exponentially with increasing volume fraction of NZF, while BST composites exhibited no statistically significant variation with volume fraction. </p> <p>For composites containing both BST and NZF, increasing the volume fraction of either inclusion increased the permittivity with a stronger dependence on BST volume fraction. Increasing NZF volume fraction increased the magnetic permeability, while changing BST volume fraction had no effect on the composite permeability. The DC dielectric breakdown voltage decreased exponentially with increased NZF volume fraction. Adding as little as 5% BST to an NZF composite more than doubled the breakdown threshold compared to a composite containing NZF alone. For example, adding 10% BST to a 15% NZF composite increased the breakdown strength by over 800%. The combination of tunability of permittivity and permeability by managing BST and NZF volume fractions with the increased dielectric breakdown strength by introducing BST make this a promising approach for designing high power nonlinear transmission lines with input pulses of hundreds of kilovolts.</p> <p>Coaxial nonlinear transmission lines are produced using composites with NZF inclusions and BST inclusions and driven by a Blumlein pulse generator with a 10 ns pulse duration and 1.5 ns risetime. Applying a 30 kV pulse using the Blumlein pulse generator resulted in frequencies ranging from 1.1 to 1.3 GHz with an output power over 20 kW from the nonlinear transmission line. The output frequencies increased with increasing volume fraction of BST, but the high power oscillations characteristic of an NLTL did not occur. Simulations using LT Spice demonstrated that an NLTL driven with a Blumlein modulator did not induce high power oscillations while driving the same NLTL with a pulse forming network did. </p> <p>Finally, a composite-based NLTL could be driven directly by a high voltage power supply without a power modulator to produce oscillations both during and after the formed pulse upon reaching a critical threshold. The output frequency of the NLTLs is 1 GHz after the pulse and ranged from 950 MHz to 2.2 GHz during the pulse. These results demonstrate that the NLTL may be used as both a pulse forming line and high power microwave source, providing a novel way to reduce device size and weight, while the use of composites could provide additional flexibility in pulse output tuning. </p>

<p>A variety of methods have been developed to enhance solid propellant burning rates, including adjusting oxidizer particle size, modifying metal additives, tailoring the propellant core geometry, and adding catalysts or wires. Fully consumable reactive wires embedded in propellant have been used to increase the burning rate by increasing the surface area; however, the manufacture of propellant grains and the observation of geometric effects with reactive components has been restricted by traditional manufacturing and viewing methods. In this work, a printable reactive filament was developed that is tailorable to a number of use cases spanning reactive fibers to photosensitive igniters. The filament employs aluminum fuel within a printable polyvinylidene fluoride matrix that can be tailored to a desired burning rate through stoichiometry or aluminum fuel configuration such as particle size and modified aluminum composites. The material is printable with fused filament fabrication, enabling access to more complex geometries such as spirals and branches that are inaccessible to traditionally cast reactive materials. However, additively manufacturing the reactive fluoropolymer and propellant together comes attendant with many challenges given the significantly different physical properties, particularly regarding adhesion. To circumvent the challenges posed by multiple printing techniques required for such dissimilar materials, the reactive fluoropolymer was included within a solid propellant carrier matrix as small fibers. The fibers were varied in aspect ratio (AR) and orientation, with aspect ratios greater than one exhibiting a self-alignment behavior in concordance with the prescribed extrusion direction. The effective burning rate of the propellant was improved nearly twofold with 10 wt.% reactive fibers with an AR of 7 and vertical orientation. </p> <p>The reactive wires and fibers in propellant proved difficult to image in realistic sample designs, given that traditional visible imaging techniques restrict the location and dimensions of the reactive wire due to the necessity of an intrusive window next to the wire, a single-view dynamic X-ray imaging technique was employed to analyze the evolution of the internal burning profile of propellant cast with embedded additively manufacture reactive components. To image complex branching geometries and propellant with multiple reactive components stacked within the same line of sight, the dynamic X-ray imaging technique was expanded to two views. Topographic reconstructions of propellants with multiple reactive fibers showed the evolution of the burning surface enhanced by the geometric effects caused by the faster burning fibers. These dual-view reconstructions provide a method for accurate quantitative analysis of volumetric burning rates that can improve the accessibility and viability of novel propellant grain designs.</p>

De nouveaux matériaux hybrides « inorganique-organique » pour le captage de polluants organiques (pesticides, HAP) ont été préparés soit par greffage sur des oxydes métalliques, soit par procédé sol-gel. Pour préparer ces matériaux nous avons développé une méthodologie catalytique pour la synthèse des motifs organiques aromatiques. Cette méthodologie repose sur la réaction de couplage de Heck palladocatalysée entre le vinylphosphonate de diéthyle avec des différents halogénures d’aryles en utilisant des catalyseurs homogènes et hétérogènes. Des bons rendements isolés ont été obtenus. En complément, nous avons étudié l’arylation du diéthylacétale de l’acroléine en milieu aqueux qui donne principalement l’ester propanoïque et le cinnamaldéhyde. Nous avons mis en évidence l’influence de différents paramètres (catalyseurs, température, bases, additifs) et montré que l’ajout de cyclodextrines est bénéfique, en augmentant dans la plupart des cas la vitesse de la réaction. Dans le cadre de cette étude, nous avons montré que le remplacement de NaOAc par NH(i-Pr)2 conduisait à une inversion de la sélectivité du cinnamaldéhyde vers l’ester propanoïque. Les matériaux azotés (amine; guanidine; biguanide@oxyde métallique) ont été obtenus soit par greffage des composés bi fonctionnels [fonction azoté]/PO(OEt)2 sur les supports, soit par greffage d’un aminophosphonate suivi d’une condensation en phase solide avec le DIP.La capacités de piégeage de différents pesticides par extraction en phase solide a été évaluée et comparés à celle de deux matériaux courants (charbon actif et Si-C18) connus comme support solide universel dans ce domaine. Nous avons ainsi démontré la complémentarité des différents matériaux dans le piégeage des pesticides. / Development of new hybrid materials “inorganic-organics” for the collecting of the various organic pollutants (pesticides, PAH). These materials were prepared by two methods: grafting of metallic oxides and sol-gel method. A catalytic methodology of the aromatic organic matrix synthesis was considered. This methodology is based on the reaction of pallado-catalyzed Heck coupling between the diethyl vinylphosphonate with different aryl halogenurs by using homogeneous and heterogeneous catalysts. The good isolated yields for products were obtained. The complement, we study of the arylation reaction of the acrolein diethylacetal in aqueous medium, and the influence of various parameters (catalysts, bases, temperature, additifs) on this reaction. The addition of cyclodextrins in reaction medium is beneficial. Within the framework of this study, we showed that the replacement of NaOAc by NH (i-Pr)2 led to an inversion of the selectivity of cinnamaldéhyde towards propanoïque ester. Nitrogen material (amine, guanide, biguanide/PO-OEt)2 either by grafting of bifunctional compounds on the supports, and grafting of amiophosphonate flow condensation to DIP.The capacity of the trapping of pesticides by extraction in solid phase was evaluated and compared of two current materials (activated carbon and Si-C18) known as universal solid support. We thus showed the complementarity of various materials in the trapping of the pesticides

Différents matériaux hybrides à base de polyoxométallates (POMs) ont été synthétisés au cours de cette thèse. Dans un premier type de matériaux, appelé POM@MOF, des POMs sont incorporés au sein des cavités poreuses d'un Metal-Organic-Framework (MOF). Ces matériaux ont été synthétisés par une méthode d'imprégnation en milieu aqueux ou par synthèse directe en conditions solvothermales. Ils ont ensuite été caractérisés de manière approfondie. La stabilité ou l'évolution des polyoxométallates lors de l'incorporation dans le MOF étant chaque fois parfaitement établie. Les matériaux POM@MOFs ont ensuite été étudiés pour leurs applications en magnétisme, pour la détection et en catalyse. Dans un second temps, des polymère de coordination hybrides à base de POMs (surnomés POMOFs) construits à partir d'isomères ε-Keggin reliés par des ligands organiques ont été synthétisés par voie hydrothermale. De nouvelles structures POMOFs ont pu être obtenue en présence de POMs, de ligands carboxylates et de complexes métalliques comme contre-ions non-innocents. L'activité de ces matériaux vis-à-vis de la réduction des protons a été étudiée par électrocatalyse et photocatalyse. Parallèlement, des synthèses de composés moléculaires solubles à base de POMs ε-Keggin ont également été réalisées. Finalement, des espèces hybrides incorporant des métaux de transitions et des ligands bisphosphonates ont été synthétisées : des polymères incorporant du cuivre(II) et un composé moléculaire à base fer(III). Ces espèces ont ensuite été étudiées pour leurs propriétés magnétiques, catalytiques pour la réduction des NOx. L'espèce à base de fer a également été sélectionnée comme substrat pour des études de dépôt sur surface de silice. / Different Polyoxometalate (POM) based hybrid materials were synthesised during this doctorate. In the first type of materials, called POM@MOF, POMs are incorporated in the porous cavities of a Metal-Organic-Framework (MOF). These materials were synthesised by a impregnation method in an aqueous medium or by direct synthesis in solvothermal conditions. They were then extensively characterised. For every material, the stability or transformation of the POMs during the incorporation was accurately established. The POM@MOFs materials were then studied for their applications in magnetism, for detection and in catalysis. In a second time, POM-based hybrid coordination polymers (called POMOFs) made from ε-Keggin isomers connected by organic linkers were synthesised by a hydrothermal method. New POMOFs structures have been obtained with POMs, carboxylate linkers and metallic complexes as non-innocents counter ions. The catalytic activity of these materials toward protons reduction was studied by electrocatalysis and photocatalysis. In parallel, syntheses of soluble molecular compounds based on ε-Keggin POMs were also performed. Finally, hybrid species incorporating transition metals and bisphosphonate linkers were synthesised : three copper(II) based polymers and a molecular coumpound incorporating iron(III). The magnetic and catalytic (reduction of NOx) properties of these materials were then studied. The iron based species was also selected as substrate for the deposition on a silica surface.

Le travail présenté dans ce mémoire porte sur la réalisation et l’étude des cellules solaires PV hybrides à réseaux interpénétrés utilisant les nanofils de silicium. Nos études ont porté essentiellement sur l’optimisation des structures hybrides à base de PVK ou de MEH-PPV mélangé dans leur volume avec une phase de nanofils de silicium, référant aux structures PVK/NFSi et MEH-PPV/NFSi respectivement. Cette étude a montré l’étroite interdépendance entre la morphologie des nanocomposites et les propriétés photovoltaïques des cellules réalisées. Nous avons étudiés l’influence de la concentration des nanofils de silicium sur le processus de dissociation des paires photo-générées. Nous avons également étudié l’effet des traitements thermiques et nous avons mis en évidence un meilleur transfert de charge dans le cas des structures PVK/NFSi. Nous avons aussi observé l’influence bénéfique de la désoxydation ainsi que le traitement de fonctionnalisation des nanofils sur l’amélioration du transfert de charge dans le cas des structures réalisées. En conclusion, nous avons montré que les cellules PV hybrides à réseaux interpénétrés utilisant les nanofils de silicium peuvent être optimisées grâce à la compréhension et au réglage fin du transfert de charges / The work presented in this thesis focuses on the implementation and study of hybrid solar cells interpenetrating networks using silicon nanowires. Our studies have focused on the optimization of hybrid structures based PVK or MEH-PPV mixed in their volume with silicon nanowires phase, referring to structures PVK/NFSI and MEH-PPV/NFSI respectively. This study showed the close interdependence between morphology and properties of nanocomposites photovoltaic cells made. We studied the influence of the concentration of silicon nanowires on the dissociation process of photo-generated pairs. We also studied the effect of heat treatment and we have demonstrated a better load transfer in the case of structures PVK/NFSI. We also observed the beneficial effect of deoxidation treatment and functionalization of the nanowires on the improvement of charge transfer in the case of structures made. In conclusion, we have shown that the PV hybrid cell using silicon nanowires can be optimized through understanding and fine tuning of the charge transfer

<p>Extrusion Deposition Additive Manufacturing (EDAM) is a process in which fiber-filled thermoplastic polymers pellets get molten in the extruder and deposited onto a build plate in a layer-by-layer basis. The use of short fiber composite for EDAM has enabled large-scale 3D printing structures and tools for traditional composite manufacturing processes. Successful EDAM production critically depends on the understanding of the process-structure-property relationship. Especially on the bonding between the beads which is of paramount importance in additive manufacturing since it affects primarily the fracture and strength characteristics of the printed part. Bonding is influenced mainly by the temperature history and the contact between the beads. Both of which is dependent on the fiber orientation within the bead induced by the flow deformation that occurs according to the printing parameters. This study aims to investigate and model the complex relationship between the printing conditions and inter-bead bonding in the lateral direction.</p> <p>A framework was developed to facilitate this aim, and it contains a fusion bonding model that couples the time-temperature history and the bead-to-bead contact interface. Four deposition parameters were studied: the nozzle height, ratio of the print velocity to extrudate velocity, bead-to-bead spacing, and layer time. First, a deposition flow model was developed, utilizing the anisotropic viscous flow model and smooth particle hydrodynamic finite element formulation, to predict the fiber orientation state across the deposited bead and the bead-to-bead interface for the given set of deposition parameters. Next, the effect of printing conditions on the temperature history of the bead was discovered by utilizing the heat transfer process simulation in ADDITIVE3D. Third, the experimental characterization procedure for mode I fracture toughness in the lateral direction was developed, and the fracture toughness was characterized using linear elastic fracture mechanics principles. Lastly, the phenomenological model for non-isothermal lateral fusion bonding was characterized using the bead contact interface, temperature history, and fracture toughness properties. This work showed a comprehensive effort in fusion bonding modeling while also presented a valuable process-structure-property-performance relationship in EDAM.  Guidance on the selection of printing conditions and strategy can be made using the developed model to print higher-strength parts.  </p>

<p>  </p> <p>Polymer bonded explosives (PBX) are a particle reinforced composite containing a high solids loading of explosive particulates bound in a polymer matrix. Commercially produced energetic particulates contain some percentage of flaws in the form of contaminants, porosity, and preexisting fractures. Additional large-scale porosity within the composite is generated during PBX formulation. The introduction of novel additive manufacturing techniques to the energetics field alters the known composite structure and introduces a porosity variable that has not been fully characterized. Porosity collapse during deformation is believed to be a predominant mechanism for hotspot formation, which dominates shock initiation behaviors. These phenomena are difficult to experimentally characterize due to inherent small spectral and temporal scales, and as such numerical and computational models are relied upon to inform fundamental physics. Experimental characterization of the behaviors of energetic materials during deformation is necessary to better inform computational studies and improve our understanding of hotspot formation mechanisms. </p> <p>This dissertation experimentally evaluates the high-rate deformation of porosity in individual explosive particulates and within the overall composite structure. This has included the development of a novel micromachining technique for pore generation in energetic single crystals using the focused ion beam (FIB), resulting in precise and controllable porosity generation that is easily reproducible in collaboration with computational studies. FIB was shown to be an effective pore generation technique, verified by assessing surface roughness and pore quality compared to contemporary manufacturing methods. Three experimental subsets are evaluated: surface cracks in HMX single crystals, polygonal pores in HMX single crystals, and large-scale porosity variations in mock vibration assisted print (VAP) produced composites of borosilicate glass beads and Sylgard 184® binder. A single stage light gas gun was used to impact the samples at 400 m/s and the impact event and resultant material response were observed in real time using x-ray phase contrast imaging (PCI). Machined surface cracks were shown to have negligible effect on the final fracture behaviors of HMX crystals. In polygonal pores fractures were shown to originate due to stress concentration during impact followed by otherwise expected brittle fracture behaviors. For wedge-like pores, the shockwave culminates on the front face of the pore and contributed to early fracture in some samples as well as a consistent open fracture opposite the impact along the shockwave direction in later stages of impact. For the blunt rectangular-like pores two differing behaviors were observed, wherein either the pore condensed and fracture at the pore was not seen during the impact event or large open fractures formed at the pore corners opposite the shockwave. The variance in response is attributed to the energy of fracture dissipating somewhere else in the material bulk, like the behaviors observed in the milled slot samples. Finally, additively manufactured PBX deformation behaviors were observed to be dominated by the collapse of the existing ordered porosity in the bulk which occurred at an increased rate relative to the bulk material compression. This resulted in a three-stage progression of deformation, consisting of a rapid collapse of large-scale ordered porosity, followed by the densification of the remaining features, and ultimately ending in compaction of the bulk as the impact projectile fully compressed the samples. Future work includes exploration of further FIB produced pore effects on dynamic fractures, evaluation of printed material deformation behaviors at additional rates, as well as application and evaluation of additional VAP printed material formulations.  </p>