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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
251

Development of a Phase Separation Strategy in Macrocyclization Reactions

Bédard, Anne-Catherine 04 1900 (has links)
La réaction de macrocyclisation est une transformation fondamentale en chimie organique de synthèse. Le principal défi associcé à la formation de macrocycles est la compétition inhérente avec la réaction d’oligomérisation qui mène à la formation de sousproduits indésirables. De plus, l’utilisation de conditions de dilutions élevées qui sont nécessaires afin d’obtenir une cyclisation “sélective”, sont souvent décourageantes pour les applications à l’échelle industrielle. Malgré cet intérêt pour les macrocycles, la recherche visant à développer des stratégies environnementalement bénignes, qui permettent d’utiliser des concentrations normales pour leur synthèse, sont encore rares. Cette thèse décrit le développement d’une nouvelle approche générale visant à améliorer l’efficacité des réactions de macrocyclisation en utilisant le contrôle des effets de dilution. Une stratégie de “séparation de phase” qui permet de réaliser des réactions à des concentrations plus élevées a été developpée. Elle se base sur un mélange de solvant aggrégé contrôlé par les propriétés du poly(éthylène glycol) (PEG). Des études de tension de surface, spectroscopie UV et tagging chimique ont été réalisées afin d’élucider le mécanisme de “séparation de phase”. Il est proposé que celui-ci fonctionne par diffusion lente du substrat organique vers la phase ou le catalyseur est actif. La nature du polymère co-solvant joue donc un rôle crutial dans le contrôle de l’aggrégation et de la catalyse La stratégie de “séparation de phase” a initiallement été étudiée en utilisant le couplage oxidatif d’alcynes de type Glaser-Hay co-catalysé par un complexe de cuivre et de nickel puis a été transposée à la chimie en flux continu. Elle fut ensuite appliquée à la cycloaddition d’alcynes et d’azotures catalysée par un complexe de cuivre en “batch” ainsi qu’en flux continu. / Macrocyclization is a fundamentally important transformation in organic synthetic chemistry. The main challenge associated with the synthesis of large ring compounds is the competing oligomerization processes that lead to unwanted side-products. Moreover, the high dilution conditions needed to achieved “selective” cyclization are often daunting for industrial applications. Despite the level of interest in macrocycles, research aimed at developing sustainable strategies that focus on catalysis at high concentrations in macrocyclization are still rare. The following thesis describes the development of a novel approach aimed at improving the efficiency of macrocyclization reactions through the control of dilution effects. A “phase separation” strategy that allows for macrocyclization to be conducted at higher concentrations was developped. It relies on an aggregated solvent mixture controlled by a poly(ethylene glycol) (PEG) co-solvent. Insight into the mechanism of “phase separation” was probed using surface tension measurments, UV spectroscopy and chemical tagging. It was proposed to function by allowing slow diffusion of an organic substrate to the phase where the catalyst is active. Consequently, the nature of the polymer co-solvent plays a role in controlling both aggregation and catalysis. The “phase separation” strategy was initially developed using the copper and nickel co-catalyzed Glaser-Hay oxidative coupling of terminal alkynes in batch and was also transposed to continuous flow conditions. The “phase separation” strategy was then applied to the copper-catalyzed alkyne-azide cycloaddition in both batch and continuous flow.
252

Analyse mathématique et numérique de plusieurs problèmes non linéaires / Mathematical and numerical analysis of some nonlinear problems

Peng, Shuiran 07 December 2018 (has links)
Cette thèse est consacrée à l’étude théorique et numérique de plusieurs équations aux dérivées partielles non linéaires qui apparaissent dans la modélisation de la séparation de phase et des micro-systèmes électro-mécaniques (MSEM). Dans la première partie, nous étudions des modèles d’ordre élevé en séparation de phase pour lesquels nous obtenons le caractère bien posé et la dissipativité, ainsi que l’existence de l’attracteur global et, dans certains cas, des simulations numériques. De manière plus précise, nous considérons dans cette première partie des modèles de type Allen-Cahn et Cahn-Hilliard d’ordre élevé avec un potentiel régulier et des modèles de type Allen-Cahn d’ordre élevé avec un potentiel logarithmique. En outre, nous étudions des modèles anisotropes d’ordre élevé et des généralisations d’ordre élevé de l’équation de Cahn-Hilliard avec des applications en biologie, traitement d’images, etc. Nous étudions également la relaxation hyperbolique d’équations de Cahn-Hilliard anisotropes d’ordre élevé. Dans la seconde partie, nous proposons des schémas semi-discrets semi-implicites et implicites et totalement discrétisés afin de résoudre l’équation aux dérivées partielles non linéaire décrivant à la fois les effets élastiques et électrostatiques de condensateurs MSEM. Nous faisons une analyse théorique de ces schémas et de la convergence sous certaines conditions. De plus, plusieurs simulations numériques illustrent et appuient les résultats théoriques. / This thesis is devoted to the theoretical and numerical study of several nonlinear partial differential equations, which occur in the mathematical modeling of phase separation and micro-electromechanical system (MEMS). In the first part, we study higher-order phase separation models for which we obtain well-posedness and dissipativity results, together with the existence of global attractors and, in certain cases, numerical simulations. More precisely, we consider in this first part higher-order Allen-Cahn and Cahn-Hilliard equations with a regular potential and higher-order Allen-Cahn equation with a logarithmic potential. Moreover, we study higher-order anisotropic models and higher-order generalized Cahn-Hilliard equations, which have applications in biology, image processing, etc. We also consider the hyperbolic relaxation of higher-order anisotropic Cahn-Hilliard equations. In the second part, we develop semi-implicit and implicit semi-discrete, as well as fully discrete, schemes for solving the nonlinear partial differential equation, which describes both the elastic and electrostatic effects in an idealized MEMS capacitor. We analyze theoretically the stability of these schemes and the convergence under certain assumptions. Furthermore, several numerical simulations illustrate and support the theoretical results.
253

On Phase Behaviours in Lipid/Polymer/Solvent/Water Systems and their Application for Formation of Lipid/Polymer Composite Particles

Imberg, Anna January 2003 (has links)
<p>A new kind of lipid/polymer composite particle, consisting of a biodegradable polymer matrix with well-defined lipid domains, has been created. The lipid used is the water-swelling lipid monoolein (MO), which forms a reversed bicontinuous cubic diamond structure in aqueous solutions. The polymer is poly(d,l-lactide-co-glycolide) (PLG), which degrades into water-soluble monomers through hydrolysis. This new particle might be a good alternative for encapsulation of active substances intended to be released over a longer period of time, i.e. sustained/retained/controlled release.</p><p>To prepare such particles can be difficult. Suitable phase behaviour and a solvent with the right properties are needed. For this reason, the phase behaviours of several different lipid/polymer/solvent/water systems have been explored. From the phase behaviour of a suitable system (i.e. MO/PLG/ethyl acetate/water), a route for formation of lipid/polymer composite particles has been deduced. Particles have been formed and distinct, water-swelling, lipid domains have been confirmed by characterization by means of confocal laser scanning probe microscopy (CLSM). </p><p>The sample preparation process has been automated and a method based on using a robotic liquid handler has been developed. Phase diagrams have been determined by examination of macroscopic behaviours and the microstructures of the phases have been studied by small- and wide-angle X-ray scattering (L<sub>3</sub>, V<sub>2</sub>, L<sub>α</sub>, L), nuclear magnetic resonance self-diffusion (L, L<sub>3</sub>), viscosimetry (L) and rheology (L). Several different theoretical models have been applied for interpretation of the results. For example, the swelling of the reversed bicontinuous cubic phases and the sponge phase have been modelled by applying the theory of infinite periodical minimal surfaces, the sponge phase has been shown to be bicontinuous according to the theory of interconnected rods and the phase behaviour of the polymer has been described by the Flory-Huggins theory. The main focus of this work (4/5) concerns phase studies in multicomponent systems from a physical-chemical point of view.</p>
254

On Phase Behaviours in Lipid/Polymer/Solvent/Water Systems and their Application for Formation of Lipid/Polymer Composite Particles

Imberg, Anna January 2003 (has links)
A new kind of lipid/polymer composite particle, consisting of a biodegradable polymer matrix with well-defined lipid domains, has been created. The lipid used is the water-swelling lipid monoolein (MO), which forms a reversed bicontinuous cubic diamond structure in aqueous solutions. The polymer is poly(d,l-lactide-co-glycolide) (PLG), which degrades into water-soluble monomers through hydrolysis. This new particle might be a good alternative for encapsulation of active substances intended to be released over a longer period of time, i.e. sustained/retained/controlled release. To prepare such particles can be difficult. Suitable phase behaviour and a solvent with the right properties are needed. For this reason, the phase behaviours of several different lipid/polymer/solvent/water systems have been explored. From the phase behaviour of a suitable system (i.e. MO/PLG/ethyl acetate/water), a route for formation of lipid/polymer composite particles has been deduced. Particles have been formed and distinct, water-swelling, lipid domains have been confirmed by characterization by means of confocal laser scanning probe microscopy (CLSM). The sample preparation process has been automated and a method based on using a robotic liquid handler has been developed. Phase diagrams have been determined by examination of macroscopic behaviours and the microstructures of the phases have been studied by small- and wide-angle X-ray scattering (L3, V2, Lα, L), nuclear magnetic resonance self-diffusion (L, L3), viscosimetry (L) and rheology (L). Several different theoretical models have been applied for interpretation of the results. For example, the swelling of the reversed bicontinuous cubic phases and the sponge phase have been modelled by applying the theory of infinite periodical minimal surfaces, the sponge phase has been shown to be bicontinuous according to the theory of interconnected rods and the phase behaviour of the polymer has been described by the Flory-Huggins theory. The main focus of this work (4/5) concerns phase studies in multicomponent systems from a physical-chemical point of view.
255

Crystallization of Parabens : Thermodynamics, Nucleation and Processing

Huaiyu, Yang January 2013 (has links)
In this work, the solubility of butyl paraben in 7 pure solvents and in 5 different ethanol-water mixtures has been determined from 1 ˚C to 50 ˚C. The solubility of ethyl paraben and propyl paraben in various solvents has been determined at 10 ˚C. The molar solubility of butyl paraben in pure solvents and its thermodynamic properties, measured by Differential Scanning Calorimetry, have been used to estimate the activity of the pure solid phase, and solution activity coefficients. More than 5000 nucleation experiments of ethyl paraben, propyl paraben and butyl paraben in ethyl acetate, acetone, methanol, ethanol, propanol and 70%, 90% ethanol aqueous solution have been performed. The induction time of each paraben has been determined at three different supersaturation levels in various solvents. The wide variation in induction time reveals the stochastic nature of nucleation. The solid-liquid interfacial energy, free energy of nucleation, nuclei critical radius and pre-exponential factor of parabens in these solvents have been determined according to the classical nucleation theory, and different methods of evaluation are compared. The interfacial energy of parabens in these solvents tends to increase with decreasing mole fraction solubility but the correlation is not very strong. The influence of solvent on nucleation of each paraben and nucleation behavior of parabens in each solvent is discussed. There is a trend in the data that the higher the boiling point of the solvent and the higher the melting point of the solute, the more difficult is the nucleation. This observation is paralleled by the fact that a metastable polymorph has a lower interfacial energy than the stable form, and that a solid compound with a higher melting point appears to have a higher solid-melt and solid-aqueous solution interfacial energy. It has been found that when a paraben is added to aqueous solutions with a certain proportion of ethanol, the solution separates into two immiscible liquid phases in equilibrium. The top layer is water-rich and the bottom layer is paraben-rich. The area in the ternary phase diagram of the liquid-liquid-phase separation region increases with increasing temperature. The area of the liquid-liquid-phase separation region decreases from butyl paraben, propyl paraben to ethyl paraben at the constant temperature. Cooling crystallization of solutions of different proportions of butyl paraben, water and ethanol have been carried out and recorded using the Focused Beam Reflectance Method, Particle Vision and Measurement, and in-situ Infrared Spectroscopy. The FBRM and IR curves and the PVM photos track the appearance of liquid-liquid phase separation and crystallization. The results suggest that the liquid-liquid phase separation has a negative influence on the crystal size distribution. The work illustrates how Process Analytical Technology (PAT) can be used to increase the understanding of complex crystallizations. By cooling crystallization of butyl paraben under conditions of liquid-liquid-phase separation, crystals consisting of a porous layer in between two solid layers have been produced. The outer layers are transparent and compact while the middle layer is full of pores. The thickness of the porous layer can reach more than half of the whole crystal. These sandwich crystals contain only one polymorph as determined by Confocal Raman Microscopy and single crystal X-Ray Diffraction. However, the middle layer material melts at lower temperature than outer layer material. / <p>QC 20130515</p> / investigate nucleation and crystallization of drug-like organic molecules
256

Investigation Of Electronic And Magnetic Structure Of Transition Metal Oxides With Emphasis On Magnetoresistive Systems

Topwal, Dinesh 06 1900 (has links)
Electronic structure of transition metal oxides has been a subject of intense research since decades due to the wide spectrum of properties that they exhibit, like high temperature superconductivity, metal-insulator transitions (MIT), phase separation etc. Among these, colossal magnetoresistance (CMR), i.e. a sharp drop in the electrical resistance by the application of an external magnetic field, is a property of fundamental and technological importance. In the present study we investigate several of these interesting properties ranging from colossal magnetoresistance, metal-insulator transitions and phase separation phenomena on a wide range of magnetoresistive systems. All these properties originate in transition metal oxides due to a competition between the strong inter-atomic Coulomb interaction strength within the transition metal d electrons and a large hopping interaction strength between the metal d and oxygen 2p states. In this thesis we report the investigation of the electronic and magnetic structures of some magnetoresistive oxides, including various double perovskites and manganites, using various high energy spectroscopies in conjunction with various theoretical approaches. The samples for the present experimental investigation were prepared by different synthetic routes, such as solid state reaction, nitrate method, d.c arc melting and float zone method, and were characterized by x-ray diffraction, four probe resistivity, magnetic susceptibility, optical absorption and energy dispersive analysis of x-rays while some of the samples were supplied by our collaborators. Various spectroscopic techniques like x-ray photoemission spectroscopy (XPS), ultraviolet photoemission spectroscopy (UPS) , bremsstrahlung isochromat spectroscopy (BIS), x-ray absorption spectroscopy (XAS), x-ray magnetic circular dichroism spectroscopy (XMCD) , electron energy loss spectroscopy (EELS), spatially resolved photoelectron spectroscopy and M¨ ossbauer spectroscopy were used to probe the samples. Theoretical methods include configuration interaction cluster approach to fit the XAS and XMCD spectra while ab initio band structure calculations along with the least-square fitting procedure was used to fit some of the valence and conduction bands. Following a general introduction in Chapter 1, the details of various experimental and theoretical techniques are discussed in Chapter 2 of this thesis. Recently, a double perovskite, Sr2FeMoO6, belonging to a general family of halfmetallic ferromagnetic oxides, has shown a spectacularly large magnetoresistance even at the room temperature and at relatively small applied magnetic fields compared to the extensively investigated class of magnetoresistive manganites. Physical properties of this compound is strongly influenced by the Fe -Mo ordering. We hence synthesized Sr2FeMoO6 sample, both with high and low degree of Fe/Mo ordering. Spectroscopic investigations of these samples suggest the presence of Fe rich and Mo rich domains of the type Sr2Fe1+xMo1−xO6 in disordered Sr2FeMoO6 at times. This prompted us to prepare bulk samples of Sr2Fe1+xMo1−xO6. In Chapter 3 we address various issues related to Fe/Mo ordering like saturation magnetization, variation of TC, and CMR as well as oxidation state of Fe and Mo in Sr2FeMoO6using this new series, ”Sr2Fe1+xMo1−xO6” as it offers a better control on the Fe/Mo bonds by controlling x. On the basis of the electron spectroscopic studies in conjunction with a configuration interaction cluster calculation model coupled with the conduction band, we claim that Fe remains in 3+oxidation state throughout the series, where as Mo changes its valency to maintain the charge neutrality. An analysis of the magnetic momentas a function of x suggests that Fe at the ”wrong” crystallographic site is coupled anti-parallel to the Fe moments at the ”correct” site. Additionally, Mo depolarizes to the extend proportional to the number of Mo sites in the near-neighbor co-ordination shell. Continuing with the double perovskites in Chapter 4 we investigate the electronic and magnetic structure of Sr2FeMoO6, Ca2FeMoO6 and Ba2FeMoO6using XAS and XMCD studies. We find that the conventional XAS and XMCD calculations based on configuration interaction of a typical fragment, FeO6in this case, is insufficient to reproduce the experimental spectrum as the compounds considered here are metallic. In order to include the non local charge transfer, we coupled FeO6 octahedra to a conduction band which mimics the Mo band. Within this model we obtained a good fit to the experimental spectrum. Chapter 5 deals with another series of double perovskite (Sr1−yCay)2FeReO6which exhibits a rich phase diagram since it undergoes a metal insulator transition (MIT) with composition at low temperatures. This system becomes more interesting due to the presence of a temperature driven MIT for higher y compositions. We find that the MIT is not related to the change in valency of Fe and Re. Analysis of the near Fermi edge valence band spectra suggests opening up of a soft gap. The main reason for MIT in this system is most likely the presence of strong electron-electron correlation between multiple electrons at the Re site, which is caused by the mismatch of the Re ionic radius and change in the crystal structure across MIT. Another issue which has been extensively investigated in this thesis is phase separation in manganites presented in Chapter 6. We use a spatially resolved, direct spectroscopic probe for electronic structure with an additional unique sensitivity to chemical compositions, to investigate high quality single crystal samples of La1/4Pr3/8Ca3/8MnO3 in the first section. This unique probe establishes the formation of distinct insulating domains embedded in the metallic host at low temperatures, significantly in the absence of any perceptible chemical inhomogeneity, with the domain-size at least an order of magnitude larger than the previous largest estimate. We also provide compelling evidence of memory effects in such domain formation and morphology, suggesting an intimate connection between these electronic domains and long-range strains, often thought to be an important ingredient in the physics of doped manganites. In second part of this chapter we discuss another system namely Eu0.5Y0.5MnO3 which undergoes a chemical phase separation forming alternate stripes of Eu rich (Y deficient) orthorhombic phase and Y rich (Eu deficient) hexagonal phases. These stripes are amazingly straight and run parallel over millimeters. One more system that we investigated is a mixture of ferromagnetic La5/8Sr3/8MnO3and insulating ferroelectric LuMnO3 taken in ratio 3:7, here too the attempt to make a single crystal resulted into a chemical phase separation forming strips of metallic La5/8Sr3/8MnO3and insulating LuMnO3 throughout the sample surface. Preliminary studies suggests that strain between the chemically and crystallographically different species may result into such interesting morphology. In Chapter 7 we study pseudo-one dimensional compounds Sr3CuIrO6 and Sr3ZnIrO6 using photo electron spectroscopy. The experimental results were fitted using band structure calculations with Full Potential Linearized Augmented Plane Wave (FP-LAPW) method.
257

Simulation der Nanostrukturbildung in Alkali-dotierten Fullerenschichten / Simulation of nanostructure formation in alkali-doped fullerene layers

Touzik, Andrei 07 March 2004 (has links) (PDF)
This work presents theoretical background for the investigation of nanostructure formation in alkali-metal doped fullerene layers. A number of computational methods are used to describe structural transformation in the fullerene layer. They include tight-binding molecular dynamics, empirical molecular dynamics, Monte-Carlo calculations as well as other methods. The doped fullerene layers show the highest superconducting critical temperature among organic superconductors. A new electrochemical method of synthesis of potassium and rubidium fullerides has been recently developed by Professor Dunsch and coworkers in the department of electrochemistry and conductive polymers at IFW Dresden. The process of electrochemical doping is accompanied by several side effects, and one of them is nanostructure formation at the surface of the fullerene layer. In the present work an explanation is given for the nanostructure formation observed recently by scanning tunnel microscopy. The corresponding model is based on the concept of spontaneous phase separation that has been realized by kinetic Monte Carlo calculations. These calculations predict instability of initially homogeneous alkali-doped fullerene layers. Due to the significant gap in the Madelung energy formation of an alkali-poor and an alkali-reach phase is expected. The results of the Monte Carlo simulations point out that the particle size of the corresponding phases remains in the nanometer range. Interpretation of experimental data for metal deposition on fullerene substrates can be easily given in the framework of the phase separation concept as well. Metal clusters of the size order 50 to 100 nm emerge in course of electrochemical copper deposition on alkali-doped fullerene layers. The electrically conductive paths through the insulating fullerene layer are probably responsible for the inhomogeneous copper deposition under electrochemical conditions. A novel computer program has been developed in course of this work, which is designed as a distributed application. It can be used for diverse conventional and kinetic Monte Carlo calculations. / Die vorliegende Arbeit präsentiert theoretische Arbeiten, die das Ziel haben, die Nanostrukturbildung in dotierten Fullerenschichten zu verstehen. Diverse Rechenmethoden wurden verwendet, um die strukturellen Umwandlungen in der Fullerenschicht zu beschreiben. Die Tight-Binding-Molekulardynamik, die empirische Molekulardynamik und Monte-Carlo-Berechnungen sowie andere Methoden sind eingeschlossen. Die dotierten Fullerenschichten zeigen die höchste supraleitende kritische Temperatur unter den organischen Supraleitern. Eine neue elektrochemische Methode der Synthese von Kalium- und Rubidium-Fulleriden wurde vor kurzem von Professor Dunsch und Mitarbeitern in der Abteilung Elektrochemie und leitfähigen Polymere am IFW Dresden entwickelt. Der Prozess der elektrochemischen Dotierung wird von mehreren Nebenprozessen begleitet, und einer davon ist die Nanostrukturbildung an der Oberfäche der Fullerenschicht. In der vorliegenden Arbeit wird eine Erklärung für die Herausbildung der Nanostrukturen, die mit Hilfe von Rastertunnelmikroskopie beobachtet wurden, gegeben. Das entsprechende Modell basiert auf dem Konzept der spontanen Phasenentmischung und wird durch kinetische Monte-Carlo-Simulationen realisiert. Diese Simulationen sagen Instabilität der zunächst homogenen Alkali-dotierten Fullerenschichten voraus. Wegen des wesentlichen Unterschieds in der Madelungenergie ist die Herausbildung einer Alkalimetall-armen und einer Alkalimetall-reichen Phase zu erwarten. Die Ergebnisse der Monte-Carlo-Simulationen weisen darauf hin, dass die Teilchengröße der entsprechenden Phasen im Nanometer-Bereich bleibt. Im Rahmen des Phasenentmischungskonzepts können auch experimentelle Daten zur Metallabscheidung auf Fullerensubstraten problemlos interpretiert werden. Bei elektrochemischer Kupferabscheidung auf Alkali-dotierten Fullerenschichten entstehen Metallcluster der Größenordnung von 50 bis 100 nm. Die elektrisch leitfähige Pfade, die in einer isolierenden Matrix auftreten, sind wahrscheinlich für die ungleichmäßige Kupferabscheidung unter elektrochemischen Bedingungen verantwortlich. Ein neuartiges Computerprogramm wurde im Rahmen dieser Arbeit entwickelt, das als eine verteilte Anwendung entworfen ist. Damit können diverse konventionelle und kinetische Monte-Carlo-Simulationen durchgeführt werden.
258

Switching of surface composition and morphology of binary polymer brushes / Schalten der Oberflächenzusammensetzung und Morphologie binärer Polymerbürsten

Usov, Denys 24 April 2004 (has links) (PDF)
Switching of surface composition and morphology of binary polymer brushes in response to changes in solvent selectivity, heating above glass transition temperatures, and contact with a rubbery stamp was studied. The binary brushes: polystyrene/poly(2-vinyl pyridine) (PS/P2VP), poly(styrene-co-2,3,4,5,6-pentafluorostyrene)/poly(methyl (meth)acrylate) (PSF/P(M)MA), and PS/PMMA were synthesized via two-step surface-initiated radical polymerization. Wetting experiments show that switching of brushes? surface composition upon exposure to solvents of various thermodynamic quality occurs faster than in 6 s. It takes longer time (5-10 min), if rate of solvent diffusion into the brush film is low. Discontinuous switching of surface composition of binary brushes is found upon exposure to binary solvents with gradually changed selectivity. X-ray Photoelectron Spectroscopy (XPS) shows quantitatively that the top brush layer (1) is dominated by respective favourite polymers after exposure to solvents of opposite selectivity and (2) comprises both brush constituents in almost symmetric ratio after exposure to non-selective solvents. Morphologies of binary brushes obtained after exposure to the solvents were studied with Atomic Force Microscopy (AFM). Local top layer composition was sensed with X-ray Photoemission Electron Microscopy (XPEEM). The morphologies are relevant to the particular solvents, reproducible, and independent on previous solvents. Phase segregation beneath the brush top layers was visualized with plasma etching. Qualitative agreement of the experimentally observed morphologies and predicted with self-consistent field theory is found. Enrichment of a binary brush top layer with the polymer providing lower surface energy takes place after annealing. Perpendicular segregation of binary brush constituents was sensed with XPEEM on perpendicular walls of imprinted elevations after wet microcontact printing.
259

Ladungs- und Orbitalordnungsphänomene in Übergangsmetalloxidverbindungen unter hydrostatischem Druck / Diffraktometrische Studien mit Synchrotronstrahlung / Charge and orbital order phenomena in transition metal oxide compounds under hydrostatic pressure

Kiele, Sven 27 March 2006 (has links) (PDF)
The thesis is dealing with the investigation of charge and orbital order and their behaviour under external pressure. Therefore, a new pressure cell has been developed which allows the observation of superlattice reflections corresponding to the order phenomena under pressure using scattering of high-energy synchrotron radiation. The maximum pressure that can be reached is 1.25 GPa. Until today there has been no possibility to conduct such studies of charge and orbital order superlattice reflections under pressure using x-ray scattering. The intensities of the reflections of the single crystalline samples are quite weak compared to fundamental peaks. Therefore the measurements are strongly affected by the absorption of the radiation in the pressure cell itself. Further difficulties result from the facts that low temperatures are needed and the sample has to be oriented in reciprocal space after being mounted into the cell. Therefore, the design of a compact clamp-type piston pressure cell was chosen here. The cell is made from a copper-beryllium alloy with the wall thickness reduced in the height of the sample volume. This allows the usage inside a closed-cycle cryostat mounted on a three-axis-diffractometer. Absorption effects are minimized due to the combination of reduced wall thickness and the usage of high energy synchrotron radiation (E = 100 keV at the beamline BW5 at HASYLAB/DESY). The new experimental technique was established and used for a study of two representatives of the transition metal oxide compounds, i.e. doped cuprates and manganites, which belong to the class of strongly correlated electron systems. The 1/8-doped cuprate La_{2-x}Ba_{x}CuO_{4} reveals an ordered state at low temperatures. Inside the CuO_{2} planes a combined order of charge stripes and antiferromagnetic spin stripes is observed. The ordering results from the interaction between charge, spin and lattice degrees of freedom. Here the lattice degrees of freedom play a major role. Particularly, a structural transition from an orthorhombic to a tetragonal symmetry is prerequisite for the observation of the ordered state. The cell constructed in this work allows a more exact analysis of the coupling between the crystal lattice and the formation of the charge and spin ordered phase. The manganite system Pr_{0.7}(Ca_{0.9}Sr_{0.1})_{0.3}MnO_{3} shows a strong magnetoresistive effect, called colossal magnetoresistance (CMR). In this system, several ordered phases can be found, which exhibit charge, spin and - since the orbital degree of freedom is also present in the manganites - additionally orbital ordering phenomena. In particular, an antiferromagnetically spin ordered insulating phase, which is connected to a charge- and orbital ordered state competes with a ferromagnetic metallic phase. This competition leads to a phase separation, which determines the properties of the sample. Both phases are strongly coupled to the lattice degrees of freedom, so that application of external pressure drastically affects the interplay between the different phases and allows a detailed study of the relation between the charge and orbital ordered phase and the crystal structure. / Die vorliegende Arbeit befaßt sich mit dem Studium der Ordnungszustände von Ladungen und Orbitalen und deren Beeinflußung durch externen Druck. Als experimentelle Neuentwicklung wurde dafür eine Druckzelle entworfen, mit deren Hilfe die Beobachtung der jeweiligen Ordnungsphänomene unter Druck mittels der Streuung hochenergetischer Synchtrotronstrahlung möglich ist. Die Zelle erlaubt die Messung der orbitalen und Ladungsüberstrukturreflexe, welche aus den geordneten Zuständen resultieren, in einem Druckbereich bis 1.25 GPa. Die experimentelle Herausforderung ergibt sich hierbei aus der Tatsache, dass die Überstrukturreflexe im Vergleich zu den fundamentalen Reflexen der einkristallinen Proben sehr schwach sind und zusätzlich durch die Absorption im Mantelmaterial der Druckzelle stark beeinträchtigt werden. Darüber hinaus soll die Zelle bei tiefen Temperaturen einsetzbar und die Probe auch innerhalb der Zelle im reziproken Raum orientierbar sein. Bei dem hier realisierten Ansatz wurde für das Design daher der Typ einer kompakten Klemmdruckzelle aus einer Kupfer-Beryllium-Legierung gewählt, deren Zellwände im Bereich des Probenvolumens reduziert wurden. Dadurch ist der Einsatz der Zelle im Inneren eines Closed-Cycle-Kryostaten auf einem Einkristall-Diffraktometer möglich. Aufgrund der geringen Wandstärke der Zelle und der Nutzung von hochenergetischer Röntgenstrahlung (E = 100 keV am Messplatz BW5 des HASYLAB/DESY) werden Absorptionseffekte minimiert. Die neue Messmethode wurde im Rahmen der Arbeit etabliert und zur Untersuchung zweier wichtiger Übergangsmetalloxidverbindungen (dotierte Kuprate, Manganate), die zur Klasse der stark korrelierten Elektronensysteme gehören, eingesetzt. Das 1/8-dotierte Kupratsystem La_{2-x}Ba_{x}CuO_{4}, weist bei tiefen Temperaturen einen statisch geordneten Zustand auf. Innerhalb der CuO_{2}-Schichten des Kristalls ergibt sich eine Ordnung, bei der sich Streifen lokalisierter Löcher und antiferromagnetische Bereiche abwechseln. Ursache dieses Zustands ist das Wechselspiel von Ladungen, Spins und strukturellen Freiheitsgraden. Dabei spielen letztere eine herausgehobene Rolle. So ist insbesondere ein struktureller Übergang von einer orthorhombischen zu einer tetragonalen Phase Voraussetzung für die Beobachtung der Ordnung. Die in dieser Arbeit aufgebaute Druckzelle erlaubt eine genauere Analyse des Zusammenhangs zwischen Struktur des Kristalls und der Ausbildung der ladungs- und spingeordneten Phase. Das Manganatsystem Pr_{0.7}(Ca_{0.9}Sr_{0.1})_{0.3}MnO_{3}, zeichnet sich durch einen sehr starken magnetoresistiven Effekt aus, der auch als kolossaler Magnetowiderstand (CMR) bezeichnet wird. Auch hier kann bei tiefen Temperaturen eine geordnete Phase beobachtet werden. Allerdings spielt in diesem System zusätzlich der orbitale Freiheitsgrad der Elektronen eine entscheidende Rolle, so dass sich eine kombinierte Ladungs- und Orbitalordnung ergibt. Diese Phase, die isolierend und zusätzlich antiferromagnetisch geordnet ist, steht im direkten Wettbewerb zu einer ferromagnetischen Phase. Aus dieser Konkurrenz ergibt sich eine Tendenz zur Phasenseparation, deren Effekte die Eigenschaften des Kristalls dominieren. Da beide Phasen stark an die strukturellen Freiheitsgrade gekoppelt sind, läßt sich das Gleichgewicht zwischen ihnen durch externen Druck beeinflussen und die Abhängigkeit der ladungs- und orbitalgeordneten Phase von den strukturellen Eigenschaften des Kristalls im Detail untersuchen.
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Laterale Organisation von Shiga Toxin gebunden an Gb3-haltige Modellmembranen / Lateral Organisation of Shiga Toxin Bound to Model Membranes Containing Gb3

Windschiegl, Barbara 23 January 2009 (has links)
No description available.

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