Capillary electrochromatography (CEC) is an analytical separation technique, coupling the electroosmotic flow principles of capillary electrophoresis (CE) with the stationary phase separation principles of high performance liquid chromatography (HPLC). The development of this technique has been slowed due to technical problems with packing capillary columns. Alteration of the stationary phase to a solid monolithic support enables ease of filling and reduces bubble formation. Polymerisation of bicontinuous microemulsions can yield porous structures that are potentially suitable for use as a stationary phase for this technique. Polymerising bicontinuous microemulsions with different compositions produce monoliths of varying pore sizes. The microemulsions consist of a hydrophobic phase and an aqueous phase. The hydrophobic phase is typically methyl or butyl methacrylate, and a cross-linker, ethylene glycol dimethacrylate. The aqueous phase consists of water and a surfactant, typically sodium dodecyl sulfate. A short chain alcohol (C3-C5) is added as a porogen which also acts as a co-surfactant to aid with the stabilisation of the microemulsion. AMPS (2-acrylamido-2-methyl-l-propane sulfonic acid), added to the aqueous phase provides a charge along the polymer backbone essential for electroosmotic flow mechanism in electrochromatography. SEM analysis shows that polymerisation in-situ yields a structure with a porous topography. Materials prepared were assessed for suitability with a variety of microemulsion compositions.

We study the formation of novel bicontinuous phases in binary mixtures of AB diblock copolymers (DBCP) using the polymeric self-consistent field theory. We predict that the bicontinuous double-diamond (DD) and plumber’s nightmare (P) phases, which are metastable phases of neat diblock copolymers, could be stablized in gyroid-forming A-minority DBCPs via the blending of specifically designed A-majority DBCPs. The mechanisms of stabilizing different bicontinuous phases are revealed by analyzing the spatial distribution of the different DBCPs. It is found that the A-majority DBCPs residing mainly in the nodes of the structure, thus alleviating the packing frustration of the A-blocks. Furthermore, a local segregation of the two DBCPs occurs at the AB interface, thus regulating the local curvature of the interfaces. A synergetic interplay of these two mechanisms results in a larger stable region of the DD and P phases via the addition of tailored A-majority DBCPs. The theoretical study provides an efficient route to obtain novel bicontinuous phases. / Thesis / Master of Science (MSc)

Nous réalisons des simulations numériques de décompositions spinodales en dessous de la température de transition vitreuse. Nous étudions l'influence de cette transition sur la séparation de phase liquide-gaz. Ces études ont été motivées pour expliquer un mécanisme de formation de gels à partir de systèmes colloïdaux ayant un potentiel d'attraction à courte portée (systèmes colloïdes/polymères non-adsorbant) mis en évidence lors de récentes expériences mais dont les raisons étaient floues. Nos résultats confirment que la structure des gels est induite par la décomposition spinodale, tandis que l'arrêt de la dynamique due à la transition vitreuse fige le système en une structure bicontinue et empêche la séparation de phase d'arriver à terme. Une étude complète (diagramme des phases, structure, distribution des longueurs, distribution des densités, longueurs caractéristiques, taille des clusters, mécanisme d'évolution) de ces systèmes en fonction du temps, de la température et de la densité est réalisée. / We realize a numerical study of spinodal decomposition under glass transition. We study the influence of glass transition on liquid-gaz phase separation. Our motivation was to explain a gel formation mecanisim of colloidal systems with short range interaction (colloid/non-adsorbing polymer system) shown in recent experiments. Their authors suggested a mecanisim taht we corroborate in this thesis. Our results confirm that gel structure is shaped by spinodal decomposition, and then glass transition slow dynamics until system get pinned in a bicontinuous structure in one hand, and avoid complete liquid-gas separation in other hand. A complete study (phase diagram, structure, length distributions, density distributions, typical lengths, cluster size, evolution mecanisim) of those systems is done in function of time, temperature and density.

Relaxation models are developed using numerical solutions of the Stochastic Liouville Equation of motion. Simplified descriptions such as the stochastic master equation is described in the context of fluorescence depolarisation experiments. Redfield theory is used in order to describe NMR relaxation in bicontinuous phases. The stochastic fluctuations in the relaxation models are accounted for using Brownian Dynamics simulation technique. A novel approach to quantitatively analyse fluorescence depolarisation experiments and to determine intramolecular distances is presented. A new Brownian Dynamics simulation technique is developed in order to characterize translational diffusion along the water lipid interface of bicontinuous cubic phases.

No description available.

Gegenstand dieser Arbeit ist es, die Temperaturbeständigkeit von bikontinuierlichen Kompositmembranen bestehend aus Zeolith 4A und Visiomer HEMATMDI zu überprüfen und das Verhalten ihrer Permeanz im Verlauf der Temperaturerhöhung zu untersuchen. Weiterhin wird ihre Verwendbarkeit für technisch und industriell relevante Prozesse der Gastrocknung nachgewiesen. Zunächst wird thermogravimetrisch untersucht, bei welcher Temperatur Zersetzungserscheinungen an der polymeren Komponente auftreten. Anschließend wird thermogravimetrisch der Wassergehalt von Zeolith 4A im Bereich dieser Temperatur bestimmt. Hierauf folgen Permeationsmessungen mit Sauerstoff und Stickstoff an der bikontinuierlichen Kompositmembran. Die Temperatur wird hierbei schrittweise bis knapp unter die Zersetzungstemperatur des Polymers erhöht. Die Eignung der Membranen zur Gastrocknung wird exemplarisch an der Trocknung von Erdgas gezeigt. Es werden die Permeanzen für Wasserdampf und Methan als Hauptbestandteil von Erdgas mittels Einzelgasmessungen experimentell bestimmt. Aus diesen Permeanzen errechnet sich die ideale Selektivität der bikontinuierlichen Kompositmembran von Wasserdampf gegenüber Methan. Mit ihrer Hilfe lässt sich die Eignung der Membran zur Trocknung von Erdgas abschätzen. / The aim of this work is to study the temperature resistance of bicontinuous composite membranes, composed zeolite 4A and Visiomer HEMATMDI, and their permeances with rising temperatures. Furthermore their suitability for gas drying is investigated.

Strukturella batterier är multifunktionella; de tillhandahåller lagring av elektrokemisk energi samtidigt som de bidrar med en lastbärande funktion. Tillsammans möjliggör detta att batteriet kan integreras i karossen hos ett elektriskt fordon eller apparat. Denna multifunktionalitet möjliggör således en avsevärd reducering i fordonets vikt. Kompositmaterialet är förstärkt av kolfiberelektroder, innesluten i en elektrolytstruktur. För att förverkliga detta koncept måste batteriets elektrolyt kunna motstå mekanisk belastning, samtidigt som den transporterar joner mellan batteriets elektroder. Denna studie syftar till att bygga vidare på konceptet av fas-separerade polymerelektrolyter, skapade från polymerisationsinducerad fasseparation via termisk härdning, vilket är en teknik utvecklad av Schneider et al. och Ihrner et al. Vidare undersöks effekten av att dels använda en elektrolytlösning baserad på EC:PC, men även att inkorporera tioler till polymernätverket. Tvärbindningsmolekylerna som användes i denna studie inkluderade trimetylolpropan tris(3-merkaptopropionat) (3TMP), pentaerythritol tetrakis(3-merkaptopropionat) (4PER), och dipentaerythritol hexakis-(3-merkaptopropionat) (6DPER). Dessa skiljer sig i antal funktionella tiolgrupper. Konduktivitet, termo-mekanisk prestanda och strukturberoende egenskaper undersöktes genom tre laborativa faser. Den första fasen behandlade inverkan på elektrolytsystemet av ändrat lösningsmedel, tiol-funktionalitet samt tiolgruppförhållandet gentemot allyl gruppen på den primära monomeren. Sampolymeren innehållandes 6DPER uppvisade bäst multifunktionalitet, varpå denna utvecklades vidare i fas två där en optimal sammansättning fastställdes som bestod utav 45 viktprocent jonlösning. I den slutliga fasen konstruerades en halv-cell baserat på den tidigare optimerade elektrolytkompositionen; den uppmätta kapaciteten visar tydlig förbättring jämfört med tidigare forskning. Resultatet som erhölls i denna studie bidrar till förståendet av strukturella batteri-elektrolyter samt den forskning som en dag kan komma att förverkliga strukturella batterier och dess tillämpningskrav. / Structural batteries are multifunctional; providing electrochemical energy storage synergistically with a load-bearing function that enables their integration into the body panels of electric devices and vehicles. Thus, massless energy can be achieved. As a composite material, it is composed of reinforcing carbon fibre electrodes embedded in an electrolyte matrix. To realize this concept, the electrolyte must simultaneously transfer mechanical load and transport ions between electrodes. The following study builds on a phase-separated polymer electrolyte, created using polymerization-induced phase separation via thermal curing, formulated by Schneider et al. and Ihrner et al.. The impact of the incorporation of thiols for copolymerization and as cross-linking agents for the polymer network was researched along with use of an EC:PC-based solvent. The three thiols studied were: trimethylolpropane tris(3-mercaptopropionate) (3TMP), pentaerythritol tetrakis(3-mercaptopropionate) (4PER), and dipentaerythritol hexakis-(3-mercaptopropionate) (6DPER). These differed in regard to the amount of thiol functional groups present. Ionic conductivity, thermo-mechanical performance and structure-property relationships were studied across 3 laboratory phases. The first phase concerned the effect of thiol-functionality, the thiol functional group ratio relative to the allyl group present in the primary monomer, and the solvent interaction. 6DPER was concluded to be the most promising cross-linking agent. During the second phase, the effect of electrolyte content was evaluated with an optimum of 45 weight% determined. The third phase concluded the study, wherein a half-cell was assembled with the optimized electrolyte formulation showing improved capacity relative to previous studies. The results developed here contribute to the understanding of structural battery electrolyte systems and their continued research to meet application demands.