Aus einkristallinem Silizium gefertigte Mikroscanner werden zunehmend in Anwendungen zur Bildprojektion, Entfernungssensorik, Spektroskopie und gezielten Strahlführung von Lasern eingesetzt, denn sie ermöglichen die Miniaturisierung und Massenfertigung optischer Systeme. Durch die statische Strahlpositionierung und zum linearen Rasterscannen in einem breiten Frequenzbereich von Null bis mehrere hundert Hertz eröffnen sogenannte quasi-statische Mikroscanner im Vergleich zu bisherigen resonant schwingenden Mikroscannern ein deutlich breiteres und flexibleres Anwendungsspektrum. Jedoch wird die Bewegung aufgrund der extrem geringen Dämpfung des Systems mit Eigenschwingungen überlagert. Daher ist die Steuerung und Regelung eine notwendige Voraussetzung für die hochdynamische und präzise Strahlführung mit quasi-statischen Mikroscannern. In dieser Arbeit werden verschiedene Steuerungs- und Regelungskonzepte für quasi-statische Mikroscanner mit elektrostatischem Kammantrieb entworfen und auf einem Echtzeitsystem mit optischer Rückführung experimentell verifiziert. Das nichtlineare mechatronische Modell wird vollständig parametrisiert und geeignete Trajektorien mit Ruckbegrenzung werden hergeleitet. Schließlich werden die Regelung des Mikroscanners mit einem Mikrocontroller durch die im Chip integrierte piezoresistive Positi-nssensorik validiert und ein 2D-Rasterscan realisiert. Als Ergebnis werden Folgerungen für den Systementwurf von quasi-statischen Mikroscannern abgeleitet.:Kurzfassung Abstract Inhaltsverzeichnis Abbildungs- und Tabellenverzeichnis Abkürzungs- und Symbolverzeichnis 1 Einleitung 1.1 Anwendungsgebiete 1.2 Antriebsprinzipien für Mikroscanner 1.3 Quasi-statische Mikroscanner des Fraunhofer IPMS 1.4 Mechatronische Modellbildung 1.4.1 Elektrostatischer Elementarwandler 1.4.2 Mechanische Beschaltung 1.4.3 Impedanzrückkopplung 2 Stand der Technik und eigene Beiträge 2.1 Steuerungs- und regelungstechnische Aspekte 2.1.1 Steuerung 2.1.2 Regelung 2.2 Präzisierung der Aufgabenstellung 2.3 Problemstellungen und eigene Beiträge 3 Modellbildung 3.1 Physikalische Modellbildung 3.1.1 Elektrisches Teilsystem 3.1.2 Mechanisches Teilsystem 3.1.3 Mechatronischer Wandler 3.2 Regelungstechnische Modellbildung 3.2.1 Kleinsignalmodell 3.2.2 Zustandsraummodell und Flachheit 3.3 Experimentelle Modellbildung 3.3.1 Bestimmung der Federsteifigkeit und der Dämpfung 3.3.2 Bestimmung der Kapazitätskennlinien 3.4 Schlussfolgerungen 4 Trajektorienentwurf 4.1 Anforderungen 4.1.1 FOURIER-Zerlegung von Dreieck- und Sägezahnfunktion 4.1.2 Überlagerung mit der Streckendynamik 4.2 Ruckbegrenzung 4.2.1 Stufentrajektorie 4.2.2 Dreieck- und Sägezahntrajektorien 4.3 Entwurf mit Regelreserve 4.3.1 Aktuationsbereich 4.3.2 Regelreserve 4.4 Schlussfolgerungen 5 Steuerungs- und Regelungsentwurf 5.1 Steuerung 5.1.1 Statische Steuerung 5.1.2 Vorfilter 5.1.3 Flachheitsbasierte Vorsteuerung 5.1.4 Simulationsergebnisse 5.1.5 Fazit 5.2 Vorauswahl geeigneter Regelungsalgorithmen 5.3 Lineare Regelung 5.3.1 Robuster PID-Regler 5.3.2 Gain-Scheduling-Regler 5.4 Nichtlineare Regelung 5.4.1 Flachheitsbasierte Regelung 5.4.2 Gleitzustandsregelung 5.4.3 Beobachterentwurf 5.4.4 Flachheitsbasierte Vorsteuerung mit Ausgangsstabilisierung 5.4.5 Fazit 5.5 Repetitive Regelung 5.5.1 Dimensionierung des Stabilitätsfilters 5.5.2 Dimensionierung des Lernfilters 5.5.3 Entwurf im linearen und nichtlinearen Regelkreis 5.6 Simulative Verifikation der Regelungsalgorithmen 5.6.1 Simulationsmodell 5.6.2 Simulationsergebnisse 5.6.3 Reglerparametrierung 5.6.4 Regelfrequenzvariation 5.6.5 Variation der Modellparameter 5.6.6 Einfluss von Messrauschen 5.7 Schlussfolgerungen 6 Experimentelle Systemverifikation und Diskussion 6.1 Messaufbau mit Echtzeitsystem 6.1.1 Messaufbau 6.1.2 Echtzeitsystem 6.1.3 Auswertung des optischen Positionsdetektors 6.2 Experimentelle Ergebnisse mit Echtzeitsystem 6.2.1 Fehlerdefinition 6.2.2 Modellverifikation 6.2.3 Ergebnisse der Steuerungsverfahren 6.2.4 Ergebnisse der Regelungsverfahren 6.3 Regelung mit Mikrocontroller 6.3.1 Mikrocontroller und Treiberelektronik 6.3.2 Integrierte piezoresistive Positionssensorik 6.3.3 Regelungsergebnisse mit Mikrocontroller 6.4 Zusammenfassende Diskussion der Ergebnisse 7 Folgerungen für den Systementwurf 7.1 Entwurfsraum 7.1.1 Dynamische Deformation 7.1.2 Stabilitätsspannung 7.1.3 Trajektorienentwurfsraum 7.2 Einsatz der Steuerung und Regelung 7.3 Varianten der Kammanordnung 8 Zusammenfassung 8.1 Erreichte Ziele 8.2 Ausblick 8.3 Abschlussfazit Literaturverzeichnis Publikationen Anhang A Modellbildung und Simulation A.1 Elemente der strukturierten Analyse A.2 Grundlagen der Elektrostatik A.3 Ausführlicher Lagrange-Formalismus A.3.1 Q-Koordinaten A.3.2 PSI-Koordinaten A.4 Kapazitätskennlinien A.5 Impedanzrückkopplung A.6 Mikroscannerparameter A.7 Regelparameter der Simulation A.8 Stabilitätsnachweis der flachheitsbasierter Vorsteuerung mit Ausgangsstabilisierung Anhang B Experimentelle Verifikation B.1 Regelparameter der Messung B.2 Spannungs- und Winkelbeschleunigungsverläufe B.3 Ergebnisse der repetitiven Regelung mit Sägezahntrajektorie B.4 Impedanzmessung der Kammkapazitäten B.5 Geräteliste Thesen / Monocrystalline silicon microscanners are increasingly used in applications for image projection, distance sensors, spectroscopy and laser beam control, because they allow the miniaturization and mass production of optical systems. With static beam positioning and linear raster scanning abilities in a wide range of zero to several hundred hertz the so-called quasi-static microscanners offer a much broader and more flexible range of applications compared to common resonantly oscillating microscanners. However, the movement is superimposed with natural oscillations due to the extremely low system damping. Therefore, an open-loop and closed-loop control is necessary for highly dynamic and accurate beam control with quasi-static microscanners. In this thesis different concepts for open-loop and closed-loop control of quasi-static microscanners with electrostatic comb drives are designed and verified experimentally on a real-time system with optical feedback. The nonlinear mechatronic model becomes completely parameterized and suitable trajectories with jerk limitation are derived. The control of the microscanner on a microcontroller with feedback by the on-chip inte-rated piezoresistive position sensors is validated realizing a 2D raster scan. As a result, conclusions for the system design are derived for quasi-static microscanners.:Kurzfassung Abstract Inhaltsverzeichnis Abbildungs- und Tabellenverzeichnis Abkürzungs- und Symbolverzeichnis 1 Einleitung 1.1 Anwendungsgebiete 1.2 Antriebsprinzipien für Mikroscanner 1.3 Quasi-statische Mikroscanner des Fraunhofer IPMS 1.4 Mechatronische Modellbildung 1.4.1 Elektrostatischer Elementarwandler 1.4.2 Mechanische Beschaltung 1.4.3 Impedanzrückkopplung 2 Stand der Technik und eigene Beiträge 2.1 Steuerungs- und regelungstechnische Aspekte 2.1.1 Steuerung 2.1.2 Regelung 2.2 Präzisierung der Aufgabenstellung 2.3 Problemstellungen und eigene Beiträge 3 Modellbildung 3.1 Physikalische Modellbildung 3.1.1 Elektrisches Teilsystem 3.1.2 Mechanisches Teilsystem 3.1.3 Mechatronischer Wandler 3.2 Regelungstechnische Modellbildung 3.2.1 Kleinsignalmodell 3.2.2 Zustandsraummodell und Flachheit 3.3 Experimentelle Modellbildung 3.3.1 Bestimmung der Federsteifigkeit und der Dämpfung 3.3.2 Bestimmung der Kapazitätskennlinien 3.4 Schlussfolgerungen 4 Trajektorienentwurf 4.1 Anforderungen 4.1.1 FOURIER-Zerlegung von Dreieck- und Sägezahnfunktion 4.1.2 Überlagerung mit der Streckendynamik 4.2 Ruckbegrenzung 4.2.1 Stufentrajektorie 4.2.2 Dreieck- und Sägezahntrajektorien 4.3 Entwurf mit Regelreserve 4.3.1 Aktuationsbereich 4.3.2 Regelreserve 4.4 Schlussfolgerungen 5 Steuerungs- und Regelungsentwurf 5.1 Steuerung 5.1.1 Statische Steuerung 5.1.2 Vorfilter 5.1.3 Flachheitsbasierte Vorsteuerung 5.1.4 Simulationsergebnisse 5.1.5 Fazit 5.2 Vorauswahl geeigneter Regelungsalgorithmen 5.3 Lineare Regelung 5.3.1 Robuster PID-Regler 5.3.2 Gain-Scheduling-Regler 5.4 Nichtlineare Regelung 5.4.1 Flachheitsbasierte Regelung 5.4.2 Gleitzustandsregelung 5.4.3 Beobachterentwurf 5.4.4 Flachheitsbasierte Vorsteuerung mit Ausgangsstabilisierung 5.4.5 Fazit 5.5 Repetitive Regelung 5.5.1 Dimensionierung des Stabilitätsfilters 5.5.2 Dimensionierung des Lernfilters 5.5.3 Entwurf im linearen und nichtlinearen Regelkreis 5.6 Simulative Verifikation der Regelungsalgorithmen 5.6.1 Simulationsmodell 5.6.2 Simulationsergebnisse 5.6.3 Reglerparametrierung 5.6.4 Regelfrequenzvariation 5.6.5 Variation der Modellparameter 5.6.6 Einfluss von Messrauschen 5.7 Schlussfolgerungen 6 Experimentelle Systemverifikation und Diskussion 6.1 Messaufbau mit Echtzeitsystem 6.1.1 Messaufbau 6.1.2 Echtzeitsystem 6.1.3 Auswertung des optischen Positionsdetektors 6.2 Experimentelle Ergebnisse mit Echtzeitsystem 6.2.1 Fehlerdefinition 6.2.2 Modellverifikation 6.2.3 Ergebnisse der Steuerungsverfahren 6.2.4 Ergebnisse der Regelungsverfahren 6.3 Regelung mit Mikrocontroller 6.3.1 Mikrocontroller und Treiberelektronik 6.3.2 Integrierte piezoresistive Positionssensorik 6.3.3 Regelungsergebnisse mit Mikrocontroller 6.4 Zusammenfassende Diskussion der Ergebnisse 7 Folgerungen für den Systementwurf 7.1 Entwurfsraum 7.1.1 Dynamische Deformation 7.1.2 Stabilitätsspannung 7.1.3 Trajektorienentwurfsraum 7.2 Einsatz der Steuerung und Regelung 7.3 Varianten der Kammanordnung 8 Zusammenfassung 8.1 Erreichte Ziele 8.2 Ausblick 8.3 Abschlussfazit Literaturverzeichnis Publikationen Anhang A Modellbildung und Simulation A.1 Elemente der strukturierten Analyse A.2 Grundlagen der Elektrostatik A.3 Ausführlicher Lagrange-Formalismus A.3.1 Q-Koordinaten A.3.2 PSI-Koordinaten A.4 Kapazitätskennlinien A.5 Impedanzrückkopplung A.6 Mikroscannerparameter A.7 Regelparameter der Simulation A.8 Stabilitätsnachweis der flachheitsbasierter Vorsteuerung mit Ausgangsstabilisierung Anhang B Experimentelle Verifikation B.1 Regelparameter der Messung B.2 Spannungs- und Winkelbeschleunigungsverläufe B.3 Ergebnisse der repetitiven Regelung mit Sägezahntrajektorie B.4 Impedanzmessung der Kammkapazitäten B.5 Geräteliste Thesen

<p>Space-based global navigation and precision timing systems are critical for modern infrastructure. Atomic clock technology has increased the precision of these systems so that they are viable for military operations, navigation, telecommunications, and finance. Advances in optical atomic clocks, based on optical frequencies, provide an opportunity for even more precise timing. Therefore, developments in chip-scale optical atomic clock technologies could lead to increased and more wide-spread application of this precision timing. One component of the optical atomic clock is the optical frequency comb which serves as an interface between optical and microwave frequencies. This thesis will cover experiments related to these optical frequency combs. A 2$\mu$m fiber laser was developed in order to test second harmonic devices required to stabilize an optical frequency comb. The laser was then employed to measure the operating wavelengths and efficiencies of non-linear devices. In addition, an analysis of the radio frequency instruments used to evaluate microwave outputs was conducted to determine whether a digital signal analyzer (oscilloscope) or an analog electronic spectrum analyzer provides more accurate results for optical frequency comb based experiments.</p>

De nouveaux glycopolymères amphiphiles en peigne de type dextrane-g-poly(méthacrylate de méthyle) ont été obtenus via une polymérisation radicalaire contrôlée par transfert d’atome (ATRP). Pour contrôler les paramètres macromoléculaires de ces glycopolymères potentiellement biocompatibles et en partie biodégradables, la stratégie de synthèse « grafting from » a été sélectionnée et appliquée selon deux voies de synthèse. La première voie comporte quatre étapes : acétylation partielle des fonctions hydroxyle du dextrane ; introduction des groupements amorceurs d’ATRP ; ATRP contrôlée du méthacrylate de méthyle dans le diméthylsulfoxyde ; hydrolyse des groupements acétate dans des conditions douces. La seconde voie de synthèse permet d’obtenir ces glycopolymères en seulement deux étapes : introduction directe des groupements amorceurs d’ATRP sur le dextrane ; ATRP contrôlée du méthacrylate de méthyle dans le diméthylsulfoxyde. Des études détaillées de chaque étape ont permis à la fois d’estimer la longueur de la chaîne de dextrane et d’assurer le contrôle de l’architecture des glycopolymères (nombre et longueur des greffons). Des études préliminaires par tensiométrie interfaciale ont permit d’évaluer le caractère tensioactif de ces glycopolymères / Synthesis of the new comb-like amphiphilic glycopolymer dextran-g-poly(methyl methacrylate) was obtained thanks to an Atom Transfert Radical Polymerization (ATRP). In order to control the macromolecular parameters of these biocompatible and partly biodegradable glycopolymers, the “grafting from” strategy was applied using two different multi-step pathways. The first one is composed of four steps: partial acetylation of dextran hydroxyl groups; introduction of initiator groups convenient for ATRP; ATRP of methyl methacrylate in dimethylsulfoxide; acetyl group deprotection under mild conditions. The second pathway allows us to obtain such glycopolymers in only two steps: direct introduction of the same initiator groups onto the dextran chain and subsequent ATRP of methyl methacrylate in dimethylsulfoxide. Throughout the synthesis, detailed studies of each step enabled us to estimate the length of the dextran backbone and to assure the control of copolymer architecture in terms of graft number and graft length. Preliminary interfacial tension measurements highlighted the surfactant properties of such glycopolymers

This thesis has the dual purpose of raising awareness of the importance of the mixing protocol on the end products of polyelectrolyte-oppositely charged surfactant systems, and to contribute to a better understanding of the properties of bottle-brush polyelectrolytes when adsorbed onto interfaces. In the first part of this thesis work, the effects of the mixing protocol and the mixing procedure on formed polyelectrolyte-oppositely charged surfactant aggregates were investigated. It was shown that the initial properties of the aggregates were highly dependent on the mixing parameters, and that the difference between the resulting aggregates persisted for long periods of time. The second part of the studies was devoted to the surface properties of a series of bottle-brush polyelectrolytes made of charged segments and segments bearing poly(ethylene oxide) side chains; particular attention was paid to the effect of side chain to charge density ratio of the polyelectrolytes. It was shown that the adsorbed mass of the polyelectrolytes, and the corresponding number of poly(ethylene oxide) bearing segments at the interface, went through a maximum as the charge density of the polyelectrolyte was increased. Also, it was found that bottle-brush polyelectrolyte layers were desorbed quite easily when subjected to salt solutions. This observation was rationalized by the unfavourable excluded volume interactions between the side chains and the entropic penalty of confining them at an interface, which weaken the strength of the binding of the polyelectrolytes to the interface. However, it was shown that the same side chains effectively protect the adsorbed layer against desorption when the layer is exposed to solutions containing an oppositely charged surfactant. Investigation of the lubrication properties of the bottle-brush polyelectrolytes in an asymmetric (mica-silica) system also related the observed favourable frictional properties to the protective nature of the side chains. The decisive factor for achieving very low coefficients of friction was found to be the concentration of the side chains in the gap between the surfaces. Interestingly, it was shown that a brush-like conformation of the bottle-brush polyelectrolyte at the interface has little effect on achieving favourable lubrication properties. However, a brush-like conformation is vital for the resilience of the adsorbed layer against the competitive adsorption of species with a higher surface affinity. / QC 20100830

<p>This thesis describes the synthesis and characterization ofbranched semi-crystalline polymers. Included in this work isthe SEC characterization of a series of dendrimers. Thebranched semi-crystalline polymers were synthesized in order toinvestigate the concept of their use as powder coatings resins.This concept being that the use of branched semi-crystallinepolymers in a UV-cured powder coating system may offer a lowertemperature alternative thus allowing the use of heat sensitivesubstrates and the added benefit of a reduced viscositycompared to linear polymers.</p><p>A series of branched poly(ε-caprolactone)’s (PCL)(degree of polymerization: 5-200) initiated from hydroxylfunctional initiators were synthesized. The final architectureswere controlled by the choice of initiator structure;specifically the dendritic initiators yielded starbranchedPCL’s while the linear initiator yielded comb-branchedPCL’s. The dendritic initiators utilized were: (1) a3rd-generation Boltorn H-30, commercially availablehyperbranched polyester with approximately 32 hydroxyl groups,(2) a 3rd-generation dendrimer with 24 hydroxyl groups, and (3)a 3rd-generation dendron with 8 hydroxyl groups. Linear PCL wassynthesized for comparison. All dendritic initiators are basedon 2,2- bis(methylol) propionic acid. The comb-branchedpolymers were initiated from a modified peroxide functionalpolyacrylate. The resins were end-capped withmethylmethacrylate in order to produce a cross-linkable system.The polymers and films were characterized using 1H NMR, 13CNMR, SEC, DMTA, DSC, FT-IR, FT-Raman, rheometry and a rheometercoupled to a UV-lamp to measure cure behavior.</p><p>The star-branched PCL’s exhibited considerably lowerviscosities than their linear counterparts with the samemolecular weight for the molecular region investigated (2-550kg mol-1). It was also found that the zero shear viscosityincreased roughly exponentially with M.</p><p>The PCL star-branched resins are semi-crystalline and theirmelting points (Tm) range from 34-50°C; films can beformed and cured below 80°C. The viscoelastic behaviourduring the cure showed that the time to reach the gel point, afew seconds, increased linearly with molecular weight. Thecrossover of G’and G’’was used as the gelpoint. Measurement of mechanical properties of films showedthat the low molecular weight polymers were amorphous whilethose with high molecular weight were crystalline after cure.The polymerization of 5,5-dimethyl-1,3-dioxane-2-one (NPC) fromoligo- and multifunctional initiators was evaluated utilizingcoordination and cationic polymerization. Two tin basedcatalysts, stannous(II) 2-ethylhexanoate and stannous(II)trifluoromethane sulfonate, were compared with fumaric acid.Fumaric acid under bulk conditions resulted in lowerpolydispersity and less chance of gelling. The synthesis ofstar-branched polymers was confirmed by SEC data. The starpolymers exhibited a Tg at 20-30°C and a Tm at about100°C.</p><p>All semi-crystalline resins exhibited a fast decrease inviscosity at Tm. Blends of combbranched semi-crystalline resinsand amorphous resins exhibited a transition behavior inbetweenthat of pure semi-crystalline resins and that of amorphousresins.</p><p>The SEC characterization of a series of dendrimers withdifferent cores and terminal groups showed that the core had animpact on the viscosimetric radius of the core while theterminal groups appeared to have no effect.</p><p><b>Keywords:</b>star-branched, semi-crystalline,comb-branched, ring-opening polymerization,poly(ε-caprolactone), dendritic, thermoset, lowtemperature curing, powder coating, UVcuring,poly(5,5-dimethyl-1,3-dioxane-2-one), size exclusionchromatography, rheology, dendritic aliphatic polyester</p>

This thesis describes the synthesis and characterization ofbranched semi-crystalline polymers. Included in this work isthe SEC characterization of a series of dendrimers. Thebranched semi-crystalline polymers were synthesized in order toinvestigate the concept of their use as powder coatings resins.This concept being that the use of branched semi-crystallinepolymers in a UV-cured powder coating system may offer a lowertemperature alternative thus allowing the use of heat sensitivesubstrates and the added benefit of a reduced viscositycompared to linear polymers. A series of branched poly(ε-caprolactone)’s (PCL)(degree of polymerization: 5-200) initiated from hydroxylfunctional initiators were synthesized. The final architectureswere controlled by the choice of initiator structure;specifically the dendritic initiators yielded starbranchedPCL’s while the linear initiator yielded comb-branchedPCL’s. The dendritic initiators utilized were: (1) a3rd-generation Boltorn H-30, commercially availablehyperbranched polyester with approximately 32 hydroxyl groups,(2) a 3rd-generation dendrimer with 24 hydroxyl groups, and (3)a 3rd-generation dendron with 8 hydroxyl groups. Linear PCL wassynthesized for comparison. All dendritic initiators are basedon 2,2- bis(methylol) propionic acid. The comb-branchedpolymers were initiated from a modified peroxide functionalpolyacrylate. The resins were end-capped withmethylmethacrylate in order to produce a cross-linkable system.The polymers and films were characterized using 1H NMR, 13CNMR, SEC, DMTA, DSC, FT-IR, FT-Raman, rheometry and a rheometercoupled to a UV-lamp to measure cure behavior. The star-branched PCL’s exhibited considerably lowerviscosities than their linear counterparts with the samemolecular weight for the molecular region investigated (2-550kg mol-1). It was also found that the zero shear viscosityincreased roughly exponentially with M. The PCL star-branched resins are semi-crystalline and theirmelting points (Tm) range from 34-50°C; films can beformed and cured below 80°C. The viscoelastic behaviourduring the cure showed that the time to reach the gel point, afew seconds, increased linearly with molecular weight. Thecrossover of G’and G’’was used as the gelpoint. Measurement of mechanical properties of films showedthat the low molecular weight polymers were amorphous whilethose with high molecular weight were crystalline after cure.The polymerization of 5,5-dimethyl-1,3-dioxane-2-one (NPC) fromoligo- and multifunctional initiators was evaluated utilizingcoordination and cationic polymerization. Two tin basedcatalysts, stannous(II) 2-ethylhexanoate and stannous(II)trifluoromethane sulfonate, were compared with fumaric acid.Fumaric acid under bulk conditions resulted in lowerpolydispersity and less chance of gelling. The synthesis ofstar-branched polymers was confirmed by SEC data. The starpolymers exhibited a Tg at 20-30°C and a Tm at about100°C. All semi-crystalline resins exhibited a fast decrease inviscosity at Tm. Blends of combbranched semi-crystalline resinsand amorphous resins exhibited a transition behavior inbetweenthat of pure semi-crystalline resins and that of amorphousresins. The SEC characterization of a series of dendrimers withdifferent cores and terminal groups showed that the core had animpact on the viscosimetric radius of the core while theterminal groups appeared to have no effect. Keywords:star-branched, semi-crystalline,comb-branched, ring-opening polymerization,poly(ε-caprolactone), dendritic, thermoset, lowtemperature curing, powder coating, UVcuring,poly(5,5-dimethyl-1,3-dioxane-2-one), size exclusionchromatography, rheology, dendritic aliphatic polyester / <p>NR 20140805</p>

La communauté de la chimie atmosphérique souffre d'un manque de mesures rapides, fiables résolues spatialement et temporellement pour un large éventail de molécules réactives (radicaux tels que NO2, OH, BrO, IO, etc). En raison de leur forte réactivité, ces molécules contrôlent largement la durée de vie et la concentration de nombreuses espèces clés dans l'atmosphère, et peuvent avoir un impact important sur le climat. Les concentrations de ces radicaux sont extrêmement faibles (ppbv ou moins) et très variable dans le temps et dans l'espace, ce qui impose un véritable défi lors de la détection. Dans la première partie de cette thèse, un spectromètre UV robuste, compacte et transportable est développé, exploitant la technique ML-CEAS pour mesurer à des niveaux très faibles (pptv et même en dessous) des molécules réactives d'importance atmosphérique, en particulier, les radicaux d'oxyde d'halogènes, afin de répondre aux besoins émergents. La technique ML-CEAS est basée sur le couplage d'un laser femtoseconde à blocage de modes à une cavité optique de haute finesse, qui agit comme un piège à photons pour augmenter l'interaction entre la lumière et l'échantillon de gaz intracavité. Cela permet d'améliorer fortement la sensibilité d'absorption. La limite de détection obtenue pour le radical IO est de 20 ppqv pour un temps d'acquisition de 5 minutes, ce qui est un résultat impressionnant. Dans la deuxième partie de cette thèse, une nouvelle technique spectroscopique est développée appelée effet Vernier, qui est également basé sur l'interaction entre un laser femtoseconde à blocage de mode et une cavité optique de haute finesse. Cette technique fournit une sensibilité de détection similaire à la technique ML-CEAS, mais l'avantage est que le nombre des éléments spectraux est donné par la finesse de la cavité optique et donc peut atteindre plusieurs dizaines de milliers. De plus, cette configuration simplifie le montage expérimental par la suppression du spectrographe qui est remplacé par une simple photodiode. Le temps d'acquisition d'un spectre peut être aussi réduit à moins d' 1 ms. / The atmospheric chemistry community suffers a lack of fast, reliable and space resolved measurements for a wide set of reactive molecules (e.g. radicals such as OH, NO3, BrO, IO, etc). Due to their high reactivity, these molecules largely control the lifetime and concentration of numerous key atmospheric species, and may have an important impact on the climate. The concentrations of such radicals are extremely low (ppbv or less) and highly variable in time and space, which imposes a real challenge during the detection. In the first part of this thesis, a compact, robust and transportable UV spectrometer is developed, exploiting the Mode-Locked Cavity Enhanced Absorption Spectroscopy (ML-CEAS) technique to measure pptv and sub-pptv levels of atmospherically important reactive molecules, in particular, halogen oxide radicals, to respond to the emerging needs. The ML-CEAS technique is based on coupling a Mode-Locked femtosecond laser to a high finesse optical cavity, which acts as a photon trap to increase the interaction between the light and the intracavity gas sample, which highly enhances the absorption sensitivity. The detection limit obtained for the IO radical is 20 ppqv (part per quadrillion), which is an impressive result. In the second part of this thesis, a new spectroscopic technique is developed, called Vernier effect, which is also based on the interaction between a mode-locked femtosecond laser with a high finesse optical cavity. This technique provides detection sensitivity similar to that of ML-CEAS technique, but the advantage is that the number of the spectral elements is given by the cavity finesse, so it can reach ten thousands, as well as this technique has a simple setup, where the spectrograph is replaced by a photodiode. Additionally, the time required to measure one output absorption spectrum can be less than 1 ms.

Les lasers à fibre de haute puissance constituent depuis une dizaine d’année un outil pertinent pour un nombre croissant d’applications. Dans le cadre d’un contrat CIFRE entre la société Eolite Systems et le laboratoire Xlim (UMR 7252 du CNRS et de l’Université de Limoges), mon projet de thèse a consisté à développer les briques technologiques de futures sources lasers / High-power fiber lasers adress an increasing number of applications since ten years. In the frame of a CIFRE contract between the company Eolite Systems and Xlim (joint laboratory between CNRS and the University of Limoges), the goal of this PhD project was to develop the technological blocs to achieve all-fibre high-power lasers emiting out of the conventional spectral band covered by existing lasers.Modal instabilities in large mode area (LMA) fibers are currently the main limitation of the fiber lasers power scaling. We have experimentally demonstrated the relevance of inner cladding aperiodic structures to efficiently delocalize higher order modes outside the gain region. A systematic study of passive fibers based on such structures has shown the single propagation of the fundamental mode over a wide wavelength range from 1 to 2 µm for dimension of core up to 85 µm. This effective mode delocalization even extends up to a core dimension of 140 µm at a 2 µm wavelength.The combination of high power picosecond fiber laser with an average power of 22.7 W and a hydrogen-filled inhibited coupling Kagome fiber allowed us to generate two Raman combs over five frequency octaves from 321 nm to 12.5 µm. These two combs are controlled by the laser pump polarization and generated an average power of 10.1 W displayed over 70 laser lines for circular pump polarization and 8.6 W over 30 lines for linear polarization. Some laser lines within these combs have been generated for the first time from high-power fiber source in the mid-infrared range. We have also demonstrated the generation of high-power line by optimizing the first vibrational Stokes at 1.8 µm with an average power of 9.3 W and a quantum efficiency of the frequency conversion stage close to 80%.

Le sujet de cette thèse concerne l'élaboration de macromonomères, de copolymères greffés et de polymères étoiles de type 'mikto-arm'. De telles architectures macromoléculaires ont été synthétisées par la combinaison de techniques de polymérisation contrôlées/vivantes telles que la polymérisation par ouverture de cycle (par métathèse) (RO(M)P) etde chimie 'click' orthogonales : cycloaddition 1,3-dipolaireazoturealcyne catalysée au cuivre (CuAAC) et thiol-ène.Dans un premier temps, des macromonomères originaux à fonctionnalité polymérisable (oxa)norbornène portant deux chaînes macromoléculaires poly(e-caprolactone) (PCL) et/ou poly(oxyde d'éthylène) (POE) ont été synthétisés par combinaison ROP/CuAAC. Les macromonomères à fonctionnalité (oxa)norbornène avec deux chaînes PCL de masse molaire moyenne en nombre (Mn) compris entre 1400 et 5000 g/mol ont été obtenus par ROP organocatalysée. La synthèse des macromonomères POE44-b-PCLn à fonctionnalité norbornène avec un bloc PCL de longueur variable (1100 g/mol <Mn< 4100 g/mol) a été réalisée par combinaison CuAAC/ROP à partir d'un POE 2000 g/mol commercial. Ces macromonomères présentent des propriétés d'auto-assemblage dans l'eau avec une concentration micellaire critique et un rayon hydrodynamique dont les valeurs augmentent avec la longueur du bloc hydrophobe PCL. Dans un second temps, la réactivité de la fonctionnalité (oxa)norbornène des macromonomères a été étudiée par spectroscopie RMN 1H, chromatographie SEC et spectrométrie MALDI-ToF. Des copolymères greffés à squelettepoly(oxa)norbornène à haute densité de greffons PCL et POE ont été obtenus par ROMP en présence d'amorceurs de Grubbs selon la stratégie "grafting through". La thiol-ène a également été utilisée avec succès pour accéder à des copolymères étoiles de type 'mikto-arm' à base de PCL, POE poly(N-isopropylacrylamide). / The objective of the present thesis was the preparation of complex macromolecules by the combination of controlled/livingpolymerization methods such as ring-opening (metathesis) polymerization (RO(M)P) and highly efficient orthogonal chemistries: copper-catalyzed azide-alkyne coupling (CuAAC) and thiol-ene reactions.In the first part of this work, a series of well-defined structural (co)polymers containing a cycloolefin (norbornene (NB) oroxanorbornene (ONB)) functionality bearing two polymer chains including poly(ε-caprolactone) (PCL) and/or poly(ethylene oxide) (PEO) have been successfully prepared using the combination of ring-opening polymerization (ROP) and CuAAC ‘click’ chemistry. Well-defined (oxa)norbornenyl-functionalized bis-PCL polymers with PCL chain ranging from 1400 to 5000 g/mol were obtained by organocatalyst-mediated ROP. Norbornenyl-functionalized PEO-b-PCL block copolymers with PCL block in the range 1100 to 4100 g/mol were synthesized from commercially available PEO 2000 g/mol by CuAAC followed by ROP of CL. The presence of a hydrophilic PEO chain and a hydrophobic PCL chain in norbornenylfunctionalizedPEO-b-PCL copolymers gives rise to self-assembling properties in water solution. Critical micellar concentrations (CMC)are in the range of 0.08 – 0.006 g/L for copolymers with PCL chain length ranging from 10 to 36 CL units, respectively. Thecorresponding micelles show hydrodynamic diameters in range of 10 – 23 nm with low polydispersities.In the second part of this work, well-defined copolymers were used to prepare bottle-brush and (mikto-arm) star copolymersthrough reactions involving the cycloolefin functionality. On the one hand, high density grafting bottle-brush copolymerspoly(oxa)norbornene-g-bisPCL, polynorbornene-g-PEO/PCL (PNB-g-(PEO/PCL)) and PNB-b-(PNB-g-(PEO/PCL)) were achieved by ROMP according to the ‘grafting through’ strategy using Grubbs’ catalysts. On the other hand, PCL, PEO, PNIPAM-based 3-arms star, 4-arms star copolymers were obtained via radical thiol-ene reactions as demonstrated by 1H NMR, SEC and MALDI-ToF MS analysis.The high reactivity of these copolymers toward ROMP and thiol-ene reactions makes them interesting candidates in order toprepare new well-defined copolymers with controlled structures and properties through highly efficient synthetic strategies.

La mousse est un matériau fascinant nous accompagnant au quotidien depuis des siècles, mais sa complexité fait qu’il est difficile de comprendre et contrôler ses propriétés. L’objet de cette thèse expérimentale est de montrer par deux exemples que si l’on contrôle les écoulements ayant lieu lors de la génération de la mousse et pendant sa vie on peut alors avoir un très bon contrôle de ses propriétés structurelles et sa stabilité. Dans la première partie j’étudie la génération de mousse constituée de bulles micrométriques par un écoulement diphasique cyclique dans un tuyau connectant deux seringues. Cette technique permet de varier la fraction liquide sans affecter les distributions de tailles de bulle. Je montre que ces distributions sont essentiellement contrôlées par la présence de constrictions dans le tuyau connectant les seringues et par les propriétés physico-chimiques de la solution moussante. Mes résultats montrent que ce n’est pas le vieillissement de la mousse mais bien les instabilités hydrodynamiques qui contrôlent la taille caractéristique des bulles. Avec diverses expériences modèles de millifluidique en régime inertiel je mets en évidence ce qui semble être un nouveau processus de fragmentation de bulles. L’accélération et la décélération des bulles lors de leur passage dans une constriction seraient le moteur de cette fragmentation. Le lien précis reste à quantifier dans de futurs travaux. Dans un second temps je montre qu’il est possible de faire des films minces, libres et d’une grande stabilité avec un fondu de copolymère en peigne de PDMS-g-PEG-PPG à température ambiante, sans ajout d’agents stabilisants. Les expériences de caractérisation indiquent que c’est un liquide newtonien ayant une faible tension de surface ne présentant pas de transition de phase à température ambiante. J’ai étudié de manière approfondie le drainage de films verticaux et horizontaux, qui se fait par un écoulement laminaire du liquide confiné entre les deux interfaces liquide/air. A l’aide d’une balance à film mince microfluidique développée pour l’étude des liquides visqueux je rapporte l’apparition de stratifications dans les films très minces. Celles-ci ont la même taille que la longueur caractéristique du fondu, lié soit à la taille du polymère, soit à une micro-séparation de phase. Le drainage et la stabilité sont donc potentiellement contrôlés par cet écoulement stratifié, mais il reste à comprendre si la stratification est la conséquence d’un simple effet de confinement ou d’une micro-séparation de phase près de l’interface. / Foam is a fascinating matter which has been broadly used for centuries, but its complexity makes it difficult to understand and control its properties. The subject of this experimental thesis is to show through two examples that by controlling the flows during the generation and lifetime of the foam its stability and structural properties may be better controlled. In the first part I study the generation of foams made of microscopic bubbles by a cyclic diphasic flow in a tube connecting two syringes. With this technique one can vary the liquid fractions without changing the bubble size distributions. I show that these distributions are mainly controlled by the presence of constrictions in the tubing connecting the syringes and by the physico-chemical properties of the foaming solution. My results show that the characteristic bubble size is not fixed by foam ageing effects but by hydrodynamic instabilities. With various millifluidic model experiments in the inertial regime I highlight what seems to be a new mechanism of bubble fragmentation. The acceleration and deceleration of the bubbles when going through a constriction would be the driving effect of this process. The precise link still has to be established. In the second part I show that it is possible to make highly stable free-standing films made of a comb-copolymer melt of PDMS-g-PEG-PPG, at room temperature, and without stabilising agents. The characterisation of this melt reveals that it is a newtonian liquid with a low surface tension and not subject to phase transitions at room temperature. I studied intensively the drainage of vertical and horizontal films, which is a laminar flow of the liquid confined between its two liquid/air interfaces. Using a millifluidic thin film pressure balance, developed for the study of viscous liquids, I report the formation of stratifications in very thin films. Theses stratifications have the same step hight than the characteristic length of the melt which we measured for the bulk, linked either to the size of the macromolecules or to micro-phase separation. The drainage and stability might be controlled by this stratified flow, but we still have to understand if it results from a simple confinement effect or from an interfacially driven micro-phase separation.