One of the major limitations in Fused Filament Fabrication (FFF), a form of additive manufacturing, is the lack of composites with superior mechanical properties. Traditionally, carbon and glass fibers are widely used to improve the physical properties of polymeric matrices. However, the blending methods lead to fiber breakage, preventing generation of long fiber reinforced filaments essential for printing load-bearing components. Our approach to improve tensile properties of the printed parts was to use in-situ composites to avoid fiber breakage during filament generation. In the filaments generated, we used thermotropic liquid crystalline polymers (TLCPs) to reinforce acrylonitrile butadiene styrene (ABS) and a high performance thermoplastic, polyphenylene sulfide (PPS). The TLCPs are composed of rod-like monomers which are highly aligned under extensional kinematics imparting excellent one-dimensional tensile properties. The tensile strength and modulus of the 40 wt.% TLCP/ABS filaments was improved by 7 and 20 times, respectively. On the other hand, the 67 wt.% TLCP/PPS filament tensile strength and modulus were improved by 2 and 12 times, respectively. The filaments were generated using dual extrusion technology to produce nearly continuously reinforced filaments and to avoid matrix degradation. Rheological tests were taken advantage of to determine the processing conditions. Dual extrusion technology allowed plasticating the matrix and the reinforcing polymer separately in different extruders. Then continuous streams of TLCP were injected below the TLCP melting temperature into the matrix polymer to avoid matrix degradation. The blend was then passed through a series of static mixers, subdividing the layers into finer streams, eventually leading to nearly continuous fibrils which were an order of magnitude lower in diameter than those of the carbon and glass fibers. The composite filaments were printed below the melting temperature of the TLCPs, and the conditions were determined to avoid the relaxation of the order in the TLCPs. On printing, a matrix-like printing performance was obtained, such that the printer was able to take sharp turns in comparison with the traditionally used fibers. Moreover, the filaments led to a significant improvement in the tensile properties on using in FFF and other conventional technologies such as injection and compression molding. / Doctor of Philosophy / In this work two thermoplastic matrices, acrylonitrile butadiene styrene (ABS) and polyphenylene sulfide (PPS), were reinforced with higher melting thermoplastics of superior properties called thermotropic liquid crystalline polymers (TLCPs). This was done so that the resulting filaments could be 3D-printed without melting the TLCPs. The goal of this work was to generate nearly continuous reinforcement in the filaments and to avoid matrix degradation, and, hence, a technology called dual extrusion technology was used for the filament generation. The temperatures required for filament generation were determined using rheology, which involves the study of flow behavior of complex fluids. Dual extrusion technology allows processing of the constituent polymers separately at different temperatures, followed by a continuous injection of multiple TLCP-streams into the matrix polymers. In addition, the use of static mixers (metallic components kept in the path of flow to striate incoming streams) leads to further divisions of the TLCP-streams which are eventually drawn by pulling to orient the TLCP phase. The resulting filaments exhibited specific properties (normalized tensile properties) higher than aluminum and contained fibers that were nearly continuous, highly oriented, and an order in magnitude lower in diameter than those of carbon and glass fiber, which are commonly used reinforcements. High alignment and lower fiber diameter are essential for printing smoother printed parts. The filaments were intended to be printed without melting the TLCPs. However, previous studies involving the use of TLCP reinforced composites in conventional technologies have reported the occurrence of orientation relaxation on postprocessing, which decreases their tensile v properties. Therefore, temperatures required for 3D printing were determined using compression molding to retain filament properties on printing to the maximum extent. On printing using an unmodified 3D printer, parts were printed by taking 180º turns during material deposition. Contrarily, the use of continuous carbon fibers required a modified 3D printer to allow impregnation during 3D printing. Moreover, the performance comparison showed that the continuous carbon fibers could not be deposited in tighter loops. The properties of the printed parts were higher than those obtained on using short fibers and approaching those of the continuous fiber composites.

Syftet med rapporten är att redovisa en studie där val av utskrivningsmetod samt passande material inom additiv tillverkning ska motiveras, för att tillverka kalibreringsformar till Bucher Emhart glass glasmaskiner. Målet med studien är att tillverka kalibreringsformarna som väger mindre än stålformarna som används idag i glasmaskinerna, detta för att minska arbetsbelastningen på personalen. Stålformarna väger ca 9kg i dagsläget. För att utesluta material och utskriftmetoder användes i första steget kravspecifikationen, och sedan användes pughs matris för att väga de material och utskrivningsmetoder som klarar kraven som ställs. För att validera materialen gjordes även en FEM analys samt en analytisk beräkning på spänningarna. Utifrån Pughs matrisen kunde det konstateras att med den data som givits att en FDM skrivare med ASA som material är mest lämpat för detta projekt. Med denna 3D-skrivare och tillhörande material fick en formhalva en vikt på ca 700g, vilket minskar avsevärt vikten som måste lyftas och således minskar arbetsbelastningen hos arbetarna.

Une technique de télédétection par spectroscopie de plasma induite par filamentation (R-FIBS pour remote filament-induced breakdown spectroscopy) est utilisée pour sonder un nuage d’aérosols aqueux contenant des sels métalliques en solution. Nous avons démontré expérimentalement que cette technique peut être utilisée efficacement pour caractériser à distance la composition d’un nuage d’aérosols. En effet, la fluorescence caractéristique de tous les ions métalliques a été observée. De plus, ces raies d’émission étroites excitées par un plasma à faible densité ont pu être identifiées simultanément sans recouvrement spectral. Les résultats obtenus démontrent qu’il est possible d’identifier et distinguer simultanément tous les composants métalliques dissous dans un tel nuage. La technique a également été testée avec succès à une distance de 70 m sur un nuage aqueux contenant du chlorure de sodium. / Remote Filament Induced Breakdown Spectroscopy (R-FIBS) was used for probing a cloud of aqueous aerosols containing a mixture of dissolved metallic salts. We demonstrated experimentally that it can be used as a sensitive sensing technique to remotely retrieve the composition of microdroplets in clouds located at a distance. In fact, fluorescence from all the metallic ions dissolved was observed. Moreover, these spectrally narrow atomic transitions excited by the low density plasma did not show any signal overlap. These characteristic spectra demonstrate that R-FIBS can be used to simultaneously recognize and distinguish every single metallic constituent dissolved inside such a cloud. The technique has been successfully tested for long range field test of 70 m with an aerosol cloud of droplets containing sodium chloride.

Submitted by Biblioteca do Instituto de Física (bif@ndc.uff.br) on 2017-07-14T19:20:36Z No. of bitstreams: 1 Marcel N Oliveira_Mestrado_UFF.pdf: 4519413 bytes, checksum: c433d3349c9b78949e508a919bf89ad8 (MD5) / Made available in DSpace on 2017-07-14T19:20:36Z (GMT). No. of bitstreams: 1 Marcel N Oliveira_Mestrado_UFF.pdf: 4519413 bytes, checksum: c433d3349c9b78949e508a919bf89ad8 (MD5) / Conselho Nacional de Desenvolvimento Científico e Tecnológico / Um filamento solar entrou em erupção no dia 1 de Novembro de 2014, com início às 04:44 UT e uma duração de cerca de três horas, resultando em uma explosão solar (flare) do de classe C2.7. O flare foi associado com o desaparecimento súbito de um grande filamento. O filamento foi ejetado para o espaço, formando um núcleo de uma emissão de massa coronal (CME). A localização da explosão foi na região sudeste do sol (perto da borda oriental do sol), isto significa que a região não é geoefetiva. Uma tempestade de radiação, isto é, partículas energéticas solares (SEP) começaram a chegar à Terra em torno de 14:00 UT, atingindo a condição do nível S1 (menor) na escala NOAA de tempestades de radiação, em 2 de Novembro. Em coincidência com o início da tempestade de radiação S1 (SEP acima de 5 MeV), os telescópios Tupi localizados no IF-UFF, em Niterói – RJ, região que está localizada dentro da Anomalia do Atlântico Sul (SAA) detectou um excesso de múons, originados por partículas (prótons) relativísticas emitidas na explosão solar. Além disso, também foi encontrado em um aumento na intensidade de partículas observado no monitor de nêutrons localizado no Polo Sul. Isto significa que houve uma propagação transversal ao campo magnético interplanetário de partículas energéticas solares. No entanto, mostra-se que a difusão perpendicular sozinha não pode explicar estas observações, é necessária uma combinação com outros processos como uma velocidade muito alta, pelo menos de uma fração dos choques CME, perto do plano da eclíptica. / A solar filament erupted on November the 1st, 2014, started at 04:44 UT with a duration of about 3 hours, resulting in a solar flare of the type C2-7. The flare was associated with the sudden disappearance of a big filament. The filament was ejected to the space, forming the nucleus of a coronal mass ejection (CME). The explosion was localized in the southeast region of the sun (near sun’s oriental border), this means that the region is not geoeffective. A radiation storm i.e solar energetic particles (SEP) started to arrive on Earth around 14:00 UT, reaching the level S1 (minor) condition on the NOAA scale of radiation storms, on November the 2nd. Coinciding with the start of the S1 radiation storm (SEP above 5 MeV), the Tupi telescopes localized in IF-UFF, Niterói – RJ, region that is localized within the South Atlantic Anomaly (SAA) detected an excess of muons, originated from relativistic particles (protons) emitted on the solar explosion. Furthermore, an increase of the intensity of particles observed on the neutron monitor localized on the south pole. This means that a transversal, to the interplanetary magnetic field, propagation of solar energetic particles occurred. Nonetheless, is shown that the perpendicular diffusion alone can not explain this observations, a combination with other processes is necessary like a very high speed, of at least a fraction of the CME shocks, around the ecliptic plane.

Le but du travail est de montrer la faisabilité du tissage de filament de très faible diamètre (de l'ordre de 10 à 25 -tm) et de matières différentes (cuivre, or, polyester...). Les essais du comportement mécanique (traction, fatigue) du micro filament de cuivre ont montré la possibilité du tissage de ce type du filament à cette échelle. A partir de ces résultats, il est possible d'entrevoir des solutions techniques de tissage pour réaliser des tissus à partir de ces filaments. Ce travail a permis donc de concevoir les différentes parties de la machine de micro tissage : système d'alimentation des fils de chame, système de formation de la foule, système d'insertion du fil de trame, système de mouvement du peigne, système d'appel et de stockage du tissu. Le système de formation de la foule de type Jacquard représente le cœur de la machine à tisser. Il lève un verrou technologique persistant depuis de très nombreuses années. Les résultats prometteurs des micros actionneurs fluidiques ont permis de montrer la faisabilité du micro tissage. Ils ont permis également de valider le procédé de la fabrication d'un bloc des plusieurs actionneurs capable de séparer les filaments de chaîne pour former la foule. Le logiciel de contrôle et de dessin conçu permet à la fois de réaliser des armures et de les compiler en format convenable pour pouvoir les transmettre à la carte de contrôle. Cette dernière permet de contrôler les différentes parties de la machine à tisser. / The aim of this work is to demonstrate the feasibility ofweaving filaments of very small diameter (about 10 to 25 -tm) made ofvarious materials (copper, gold, polyester, etc...). The possibility of weaving copper micro filaments at this scale has been proved via the fatigue and traction mechanical tests. According to these results, it was possible to foresee weaving technical solutions to produce fabrics from these micro filaments. This work has permitted the design of the different parts of the micro weaving machine: warp let-off system, warp shedding system, filling insertion system, beat-up system and take-up system. Warp shedding system of Jacquard type represents the heart of the weaving machine. It solved the complicated technical problem ofweaving materials that persists since many years. The positive results of micro fluidic actuators have demonstrated the feasibility of micro weaving. They have also validated the process of manufacturing a block of severa! actuators capable of separating the warp filament's to form the shed. The created software of control and design allows to make weaves and to compile them into a convenient format to be transmitted to the control card. This card controls the different parts of the weaving machine.

In den letzten 20 Jahren näherte sich der einst nur für die Luft- und Raumfahrt entwickelte kohlenstofffaserverstärkter Kunststoff (CFK) mehr und mehr der industriellen Umsetzung in anderen Bereichen an. Die CFK-Halbzeuge und -Bauteile sind nun auch preislich in der Lage, unter Anwendung angepasster Fertigungsverfahren breiter eingesetzt zu werden. Der Fokus dieser Arbeit richtet sich exemplarisch auf die kosten- und energieeffiziente Herstellung von schnell laufenden CFK-Verbundwalzen und soll aufzeigen, dass Kostenersparnisse über Leane Fertigungsmethoden auch in der FKV-Industrie von großem Vorteil sind. Somit liefert diese Dissertationsschrift einen beispielgebenden Beitrag für den Durchbruch von Faserverbund-werkstoffen im industriellen Bereich. Darüber hinaus werden durch Prozessoptimierung Alternativen aufgezeigt, qualitativ hochwertigere und gleichsam kosteneffiziente Bauteile herzustellen.

This PhD is devoted to the mechanics and statistical mechanics of biofilaments and their most widespread model, the Worm-Like Chain (WLC) model, which, as it turns out, needs to be extended. We study the WLC in 2-d in the presence of obstacles closer than their persistence length. We characterize the short time motion by numerical simulations complemented by analytical calculations. Similar concepts serve to describe grafted DNAs swept by the front of a spreading vesicle whose adhesion is promoted by biotin/streptavidin bonds, which constrain the DNAs on narrow paths where they can be imaged. Microtubules (MT), here stabilized by taxol, show features which cannot be rationalized by the WLC and shall be related to their internal structure : i)lateral deflections of a clamped MT correspond to an effective persistence length growing with the MT size ii) MT adopt super-helical shapes. These two points are proven by refined image analysis. We analyze shape transitions correlated along the MT which are compatible with a model based on dimer bi-stability. Finally, a super helical chain model (HWLC) allowing for spontaneous curvature and twist is developed which extends the WLC. When confined to 2-d, the HWLC can adopt a ground state which is circular or wavy with inflection points where twist accumulates, so-called twist-kinks. In the circular case there exist close metastable states, with a small number of twist-kinks, which are hyperflexible.

La mémoire NAND Flash représente une part importante dans le marché des circuits intégrés et a bénéficié de la traditionnelle miniaturisation de l’industrie des sémiconducteurs lui permettant un niveau d’intégration élevé. Toutefois, cette miniaturisation semble poser des sérieux problèmes au-delà du noeud 22 nm. Dans un souci de dépasser cette limite, des solutions mémoires alternatives sont proposées parmi lesquelles la mémoire résistive (RRAM) se pose comme un sérieux candidat pour le remplacement de NAND Flash. Ainsi, dans cette thèse nous essayons de répondre à des nombreuses questions ouvertes sur les dispositifs RRAM à base d’oxyde d’hafnium (HfO2) en particulier en adressant le manque de compréhension physique détaillée sur leur fonctionnement et leur fiabilité. L’impact de la réduction de taille des RRAM, le rôle des électrodes et le processus de formation et de diffusion des défauts sont étudiés. L’impact de l’alliage/dopage de HfO2 avec d’autres matériaux pour l’optimisation des RRAM est aussi abordé. Enfin, notre étude tente de donner quelques réponses sur la formation du filament conducteur, sa stabilité et sa possible composition. / Among non-volatile memory technologies, NAND Flash represents a significant portion in the IC market and has benefitted from the traditional scaling of semiconductor industry allowing its high density integration. However, this scaling seems to be problematic beyond the 22 nm node. In an effort to go beyond this scaling limitation, alternative memory solutions are proposed among which Resistive RAM (RRAM) stands out as a serious candidate for NAND Flash replacement. Hence, in this PhD thesis we try to respond to many open questions about RRAM devices based on hafnium oxide (HfO2), in particular, by addressing the lack of detailed physical comprehension about their operation and reliability. The impact of scaling, the role of electrodes, the process of defects formation and diffusion are investigated. The impact of alloying/doping HfO2 with other materials for improved RRAM performance is also studied. Finally, our study attempts to provide some answers on the conductive filament formation, its stability and possible composition.

Les phénomènes interfaciaux impliqués dans les écoulements polyphasiques existent dans de nombreux procédés industriels. Des gouttes et des bulles sont des éléments typiques pour comprendre les phénomènes interfaciaux. Ainsi, cette thèse étudie les gouttes (bulles) impliquées dans la manipulation d’une interface, y compris la rupture de l'interface, le mouvement d’une goutte sur une surface superhydrophobe et le contact sur un support solide à l’aide d’un système d'acquisition pour des signaux électriques. Dans la première partie, une caméra rapide est utilisée pour étudier la dynamique de pincement des fluides homogènes et des ferrrofluides hétérogènes à travers des systèmes confinés et non-confinés liquide-liquide ou liquide-gaz. L'effet de compétition entre les différentes forces telles que la poussée d’Archimède, la force magnétique, la gravité et la tension interfaciale sur la rupture finale d’un fluide interne dans un environnement fluide externe est démontré et quantifié. La deuxième partie est consacrée à la manipulation d’une goutte aqueuse à l’aide d’une interface superhydrophobe sous deux angles distincts : saut d’obstacle de la goutte sur une surface solide revêtue d’une couche superhydrophobe ; déshabillement d’une goutte enveloppée de particules superhydrophobes dite "marbre liquide" sur un film huileux. Le comportement dynamique du saut d’obstacle et du déshabillement des gouttes est quantifié et comparé dans des conditions opératoires très différentes telles que la viscosité, la tension interfaciale, la géométrie d’obstacle, etc. La troisième partie est dévolue au contact d’une goutte sur un support solide: contact initial, étalement, et pincement final des fluides tant newtoniens que non newtoniens, grâce à une méthodologie combinant la caméra rapide et un système d'acquisition ultra-rapide d’un signal électrique / The interfacial phenomena in multiphase flows widely exist in numerous industrial processes. Drops and bubbles are typical models to investigate these interfacial phenomena. Thus this thesis investigates the drop (bubble) involved interface manipulation, including the breakup of interface, drop’s motion on superhydrophobic surface and Dripping-on-Substrate with an acquisition system of electric signals. In the first part, the pinch-off dynamics of homogenous fluids and heterogeneous ferrrofluids, unconfined liquid-liquid (liquid-gas) or confined liquid-liquid systems was investigated by a high-speed camera. The effect of buoyancy, magnetic force, gravity and interface tension between internal and external fluids on the final pinch-off was demonstrated and quantified. The second part focuses on the drop manipulation on superhydrophobic interface through two distinct approaches: superhydrophobic coating on a substrate and superhydrophobic particles enveloping a liquid drop to form “liquid marble”. The hurdling behavior of liquid drops on superhydrophobic obstacles and undressing dynamics of liquid marbles on oil films were discussed and the slope motion of liquid drops and liquid marbles were then compared. The third part concentrates on the Dripping-on- Substrate behavior: initial contact and spreading on a solid surface, final pinch-off of Newtonian fluids and filament thinning of non-Newtonian fluids, through a methodology combining the high-speed camera and ultra-high-speed acquisition device of an electric signal

Many active processes in cells are driven by highly specialised motor proteins, which interact with the cytoskeleton: a network of filamentous structures, e.~g.~ actin filaments and microtubules, which organises intracellular transport and largely determines the cell shape. These motor proteins are able to transduce the chemical energy, stored in ATP molecules, to do mechanical work while interacting with a filament. Certain motor proteins, e.~g.~members of the KIN-13 kinesin subfamily, are able to interact specifically with filament ends and induce depolymerisation of the filament ends. One important role for KIN-13 family members is in the mitotic spindle, a microtubule structure that is formed in the process of cell division and is responsible for separation and distribution of the duplicated genetic material to the forming daughter cells. The aim of this work is to develop a theoretical framework capable of describing experimentally observed behaviour and shed light on underlying principles of motor induced filament depolymerisation. We use two different theoretical approaches to describe motor dynamics in this non- equilibrium situation: On the one hand we use phenomenological continuum equations which themselves are to a large extent independent of the underlying molecular details of the system. Molecular details of the system are incorporated in the equations through the specific values of macroscopic parameters which are determined by the underlying details. On the other hand, we use one- and two-dimensional discrete stochastic descriptions of motors on a filament. These kind of descriptions enable us to investigate the effects of different microscopic mechanisms of filament depolymerisation, and to investigate the role of fluctuations on the dynamic behaviour of motor proteins. We additionally discuss filament depolymerisation in the case where motors are not free to move but are fixed to a common anchoring point and depolymerise filaments under the influence of applied forces, mimicking the situation in the mitotic spindle. Our results can be related to recent experiments on members of the KIN-13 subfamily and predictions made in our theory can be tested by further experiments. Although motivated by experiments involving members of the KIN-13 subfamily, our theory is not restricted to these motors but applies in general to associated proteins which regulate dynamics of filament ends.