Universität Stuttgart
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Item Open Access Untersuchungen zur Derivatisierung und Charakterisierung Carben-analoger N-heterozyklischer Halogenarsane(2021) Bender, Johannes; Gudat, Dietrich (Prof. Dr. Dr.)Die Chemie neutraler N-heterozyklischer Arsane konnte durch Synthese einer Reihe von Verbindungen mit funktionellen Substituenten am Arsen (Halogeno-, Pseudohalogeno-substituiert) erweitert sowie strukturelle und elektronische Verhältnisse aufgeklärt werden. Aus 2-Chloro-1,3,2-Diazaarsolidinen und -1,3,2-Diazaarsolenen konnten einige neue kationische Arsen-Analoga von N-heterozyklischen Carbenen hergestellt werden. Des Weiteren konnten noch unbekannte 2-Thiolato- und 2-Xanthogenato-1,3,2-Diazaarsolidine und -1,3,2-Diazaarsolene dargestellt und charakterisiert werden.Item Open Access Miscibility, viscoelastic reinforcement, and transport properties of blend membranes based on sulfonated poly(phenylene sulfone)s(2021) Saatkamp, Torben; Maier, Joachim (Prof. Dr.)Chemical energy that hydrogen may generate during combustion and the corresponding electrical energy are interconvertible by means of a fuel cell (FC) and by the electrolysis of water (WE), which allows for the utilization of the complementary nature of these two key energy vectors towards energy sustainability. A proton exchange membrane (PEM) made from an ionomer is commonly employed as the electrolyte in mobile fuel cell applications and in water electrolyzers that require dynamic operability and pressurized product gases. New PEM materials are needed to increase performance, reduce environmental impact, and allow for a more targeted design of PEMFC and PEMWE systems, all of which is in some way limited by the use of the established perfluorosulfonic acid (PFSA) type ionomers. This work’s focus lies on sulfonated poly(phenylene sulfone)s (sPPS), a unique group of fluorine-free cation conducting ionomers. They are unique in terms of their chemical stability and transport properties, however, typical in terms of their salt-like brittleness in the dry state and extensive swelling at high humidity and in water. To make the unique properties of sPPS available in application, the goal of this work is to take a comprehensive approach to their viscoelastic reinforcement. Therefore, the structure of this thesis entails three related aspects along the process from pure materials to the optimization of robust PEMs for application. The first chapter focuses on the optimization of the intrinsic viscoelastic properties of a particularly suited sPPS (termed S360, with IEC 2.78 meq g-1, EW 360 g mol-1) which lays the groundwork for reliable and systematic further development. To achieve this, relevant properties of S360 are first characterized and viscoelastic shortcomings as seen in water uptake measurements and tensile tests under dry conditions (≤ 30% relative humidity, RH) discussed. The step-growth polymerization of S360 is optimized after finding significant inorganic contamination retained in the established purification process of the widely used monomer sulfonated difluorodiphenyl sulfone (sDFDPS), allowing for the preparation of the ionomer in reproducible high molecular weight. Relevant properties of high molecular weight S360 are characterized and an enhancement of mechanical properties at 30% RH as well as when submerged in water is found. Access to reproducible high quality of S360 enables its first-time use and study as a PEM in a completely fluorine-free WE cell. At 80 °C, record performance amongst fluorine free electrolytes in PEMWEs of 3.48 A cm-2 at 1.8 V is achieved, showcasing the potential of sPPS for application. The second chapter entails the identification and better understanding of a suitable and versatile reinforcement concept for creating robust membranes based on sPPS. To achieve this, the established homogeneously miscible acid-base polymer blends of sulfonated ionomers with poly(benzimidazole) (PBI, and its derivatives PBIO and PBIOO) are discussed in-depth and chosen for later systematic optimization in combination with sPPS. Since the origin of miscibility in PBI blends with sulfonated ionomers is insufficiently described in literature and could facilitate targeted design of new blend components, a model acid-base polymer blend system comprising pyridine-functionalized poly(sulfone) (PSU) is created. Pyridine groups of different basicity tethered to PSU in varying concentration are used to investigate the effect that interpolymer acid-base interaction strength and concentration have on miscibility in blends with 80 wt% S360, as derived from the blend membranes’ cross-sectional SEMs. High mutual compatibility is achieved at high concentration of weak interpolymer interaction, which is interpreted with regards to the observed miscibility in PBI blends. Based on the derived role that hydrogen bonds may play in PBI blends, the difference of interpolymer interaction in solution (during membrane formation) and in the dry membrane is described. This could enable the development of new blend concepts in the future. An exemplary miscible blend that comprises interpolymer hydrogen bonds only in solution but not in the final membrane is shown. The third chapter describes the optimization and balance of properties in the previously described polymer blends with PBIO, following the goal to prepare membranes which can be evaluated in fuel cells and fabricated on a wider scale in order to bring the attractive properties of sPPS into application. To achieve this, S360-blend membranes of varying PBIO content are characterized with regard to conductivity and mechanical properties in various conditions. High mechanical robustness is achieved in S360 blends with 30 wt% PBIO but is accompanied by dramatic reduction of conductivity, due to the charge-consuming acid-base interaction. The findings are translated into blends with fully sulfonated sPPS (termed S220, with IEC 4.54 meq g-1, EW 220 g mol-1) which allows for the creation of membranes that combine mechanical toughness with high conductivity at a ratio of 25 wt% PBIO in S220, making the material suited for production on a commercial casting line and fuel cell testing. Membranes based on S360 that comprise 15 wt% PBIO are designated for further studies in PEMWEs, where membrane requirements differ significantly from that in PEMFCs, highlighting the versatility of the reinforcement approach chosen in this work. Finally, first fuel cell tests of thin spray coated PBIO blend membranes are conducted, and initial durability testing of sPPS-based membranes in fuel cells is possible. Overall, the results presented in this work are strongly interrelated which underlines the importance of comprehensiveness in the successful viscoelastic reinforcement of sulfonated poly(phenylene sulfone)s. Ultimately, the blend membranes resulting from this work can be used as a platform for further development of sPPS-based PEMs in the future.Item Open Access Template controlled mineralization of functional ZnO thin films(2017) Blumenstein, Nina; Bill, Joachim (Prof. Dr.)In this thesis, the influence of different organic templates on the bioinspired deposition of ZnO thin films is investigated. Depending on the polarity of the templates, the growth and the properties of the films can be influenced. On a non-polar template, film growth is inhibited whereas homogeneous films grow on polar templates. Additionally, it was shown that on a template with high polarity a crystallographic texture is observed. This leads to a macroscopically measurable piezoelectric response of these samples. In the last part of this work, the incorporation of Al, Ga and In into the ZnO films was investigated. Measurements showed a blue shift of the UV photoluminescence emission and an improved electrical conductivity with increasing doping content.Item Open Access Enzymatische Hydratisierung kurzkettiger Fettsäuren und Alkene(2018) Demming, Rebecca M.; Hauer, Bernhard (Prof. Dr.)Item Open Access Novel X-ray lenses for direct and coherent imaging(2019) Sanli, Umut Tunca; Schütz, Gisela (Prof. Dr.)Item Open Access Charakterisierung umweltneutraler, natürlicher eisenhaltiger Sauerstoffträger für Chemical-Looping-Combustion (CLC)-Kraftwerke(2018) Schopf, Alexander; Massonne, Hans-Joachim (Prof. Dr.)Chemical Looping Combustion (CLC) ist eine großtechnische Verbrennungstechnologie zur Stromerzeugung mittels Wirbelschichtreaktoren unter Verwendung von Feststoffen anstelle von Luft als Sauerstoffträger. CLC zählt zu den CO2-Sequestrierungsverfahren für Carbon Dioxide Capture and Storage (CCS). Das Rauchgas besteht hauptsächlich aus Wasserdampf und Kohlenstoffdioxid, die Produktion von Stickoxiden wird prozessbedingt vermieden, der Wirkungsgradverlust liegt bei theoretisch 2 bis 3 %. Das bislang als Sauerstoffträger für CLC verwendete Mineral Ilmenit ist im Vergleich mit anderen Erzen relativ selten. Synthetisch hergestellte Sauerstoffträger sind dagegen teurer und daher unwirtschaftlich. Ziel der Arbeit war die Identifikation umweltneutraler natürlicher Sauerstoffträger für CLC-Kraftwerke die sowohl gut verfügbar sind als auch wirtschaftliche Alternativen darstellen. Für die Untersuchungen wurden die Gütekriterien der Effektivität für CLC und Kraftwerkseignung zu Grunde gelegt: gute Abriebfestigkeit, hohe Reaktivität mit Brenngasen bei 900 °C, insbesondere Methan, hohe Sauerstofftransportkapazität mit ca. 10 % Masseverlust bei der Reduktion, hohe Reaktivität mit Luftsauerstoff bei der Oxidation und eine Temperaturstabilität von mindestens 1000 °C unter oxidierenden Bedingungen. Weiteres Forschungsziel war die Aufklärung der ablaufenden Prozesse der Reduktions- bzw. Oxidations-Reaktionen bei den einzelnen Sauerstoffträgern unter simulierten Kraftwerksbedingungen. Mit der Entwicklung eines systematischen, für alle Sauerstoffträger anwendbaren, Untersuchungsgangs wurde eine fundamentale Methode zur Visualisierung der inhärenten chemischen Reaktionen bei wiederholender sukzessiver Reduktion und Oxidation geschaffen. Die experimentelle Versuchsabfolge gliederte sich in vier Teile: Vorbereitung und mineralogische Untersuchung zur Beschreibung des Ausgangsmaterials, Vorstudie zur Überprüfung der Temperaturstabilität von 1000 °C in der Thermowaage (TGA), Hauptstudie mit Simulation von CLC in der TGA und eine Vergleichsstudie unter Kraftwerksbedingungen im Versuchskraftwerk des Instituts für Feuerungs- und Kraftwerkstechnik der Universität Stuttgart zur Korrelation der Ergebnisse der Hauptstudie. Unter ihrer Anwendung wurden die hier einbezogenen Proben charakterisiert, wobei sich sieben von 12 Proben der Hauptstudie (aufgrund der formulierten Anforderungskriterien) als Sauerstoffträger besonders geeignet erwiesen: Magnetiterz, Maphopha (RSA), Magnetiterz, Thạch Khê (SGA), Roter Glaskopf, Toulkine (IMI), MIOX ME400, Waldenstein (KMI), Hämatiterz, Norwegen (DH), Bändereisenerz, Bogalatladi (RSA) und Ilmeniterz, Capel (IFK). Bei sehr lang gewählten Reduktionszeiten mit Brenngas entstanden zudem Varietäten des Kohlenstoffs, wie bspw. amorpher Kohlenstoff, Graphit und Graphen, als Abscheidung aus der Gasphase auf den Sauerstoffträgeroberflächen. Dies gibt Anlass zu weiteren Forschungen.Item Open Access Hydrogen transport in thin films : Mg-MgH2 and Ti-TiH2 systems(2018) Hadjixenophontos, EfiHydrogen storage has become progressively important due to increasing energy demand. Magne-sium (Mg/MgH2) is one of the most promising elements of hydrogen uptake, however, the slow kinetics and need for high temperatures during dehydrogenation make this material challenging for mobile applications. Meanwhile, Titanium (Ti/TiH2/TiO2) draws attention due to its catalytic effect in hydrogenation of other metals with higher capacities. A comprehensive way to quantitatively char-acterize the kinetics of hydride formation in both systems (Mg and Ti) is shown here. A technique allowing a large range of pressures and temperatures (room temperature to 300 °C and from 0.05 bar up to 100 bar) is developed successfully. Thin films (50-1000 nm), deposited by ion beam sput-tering (PVD), are used because of their smooth surface and defined structure. In order to study hydrogen transport precisely, X-ray diffraction (XRD), electron microscopy (SEM/FIB/TEM) and electric resistance measurements are used. In the case of Mg, while a Pd coating is used as catalyst, the hydride is formed from the surface towards the substrate and transformation in the morpholo-gy is observed. Parabolic law is followed and the diffusion coefficient of hydrogen in MgH2 is ob-tained at room temperature (2.67 · 10-17 cm2/s). Additionally, a model is created to fit the experi-mental change in resistance during hydrogen loading and shows the changes in the behavior of thicker layers. The interface between Pd/Mg is discussed, since Mg5Pd2 and Mg6Pd are formed at high temperatures and are most dominant over dehydrogenation. However, at room temperature, this interface appears to be more stable. The activation energy of hydrogenation is calculated ex-perimentally from an Arrhenius plot to be equal to Ea = 22.6 ± 2.0 kJ/mol and the pre-factor D0 = 3904 cm2/s. Additional attention is given to magnesium hydride as an anode electrode in Li-ion bat-teries. TEM investigations of thin film electrodes demonstrate the complete lithiation of the mate-rial however, with drastic volume changes, leading to bad reversibility. In Ti the thin oxide layer naturally formed on the surface, appears to play a dominant role in the kinetics of hydrogen transport leading to a linear kinetics. A pressure dependency is observed, while an experimental evaluation of the permeation coefficient in the oxide is also discussed. Important information on the hydrogen transport is obtained in both systems, giving an input for further improvements of such hydrides.Item Open Access Oleathydratase katalysierte stereoselektive Hydratisierungsreaktionen kurzkettiger Alkene(2025) Härterich, Natalie; Hauer, Bernhard (Prof. Dr.)Item Open Access Gold nanoparticle-mediated DNA origami nanoarchitectures(2024) Peil, Andreas; Na Liu, Laura (Prof. Dr.)Since its origin in the 1980s, DNA (deoxyribonucleic acid) nanotechnology has established itself as a captivating nanofabrication technique with ever increasing impact that combines aspects from physics, chemistry, and biology to construct artificial nanosystems by means of molecular self assembly. Within the field of DNA nanotechnology, the DNA origami technique represents one of the most versatile fabrication tools to craft functional two-dimensional (2D) and three-dimensional (3D) nanostructures from the bottom up. These structures offer precisely tailored geometries along with programmable functions, featuring positional addressability with sub-5 nm resolution and exceptional spatiotemporal accuracy. This thesis discusses strategies to employ the DNA origami technique to assemble intricate hybrid nanosystems with synergistically integrated gold nanoparticles (AuNPs). The AuNPs take over different roles; they grant (i) structural and (ii) functional features and enable the (iii) optical monitoring of the systems. This approach allows the fabrication of nanostructures piece by piece to explore their structural and functional properties at the nanoscale in detail. The first publication covers different strategies for the hierarchical assembly of topological DNA origami structures using a AuNP-templated self-assembly approach. The assembly of [2], [3], and [4]catenanes with interconnecting AuNPs is elucidated. The AuNPs can be controllably released to disconnect the individual rings, leaving only the mechanical bond of the catenane chain. In the second publication, a dynamic AuNP-DNA origami gear system is presented that is designed to emulate a planetary gearset with precise spatiotemporal control over its rotation dynamics. The AuNPs serve three crucial tasks. They (i) structurally link the origami ring modules, (ii) mediate the rotation and (iii) enable the real time optical tracking of the rotation via fluorescence spectroscopy. The system enables tightly orchestrated and programmable bidirectional rotations. In the third publication, reconfigurable chiral metastructures comprising multiple plasmonic particles that are accurately positioned in a helical manner around a DNA origami template are discussed. The implementation of a DNA ‘swingarm strategy’ enables the simultaneous and efficient relocation of multiple closely spaced AuNPs over large distances to precisely tune the chiroptical response of the system. The presented publications illustrate the beneficial synergies between DNA origami systems and rationally integrated AuNPs with the aim to advance and expand the application spectrum of these hybrid nanosystems within their scientific disciplines.Item Open Access Modeling and simulation of closed low-pressure adsorbers for thermal energy storage(2019) Schäfer, Micha; Thess, André (Prof. Dr. rer. nat.)Closed low-pressure adsorption systems can be applied for thermal energy storage. Their performance is determined by the mass and heat transport processes in the adsorber. Therefore, thorough knowledge of these transport processes is required for further storage development. The present thesis contributes to this by providing detailed models of closed low-pressure adsorbers and by conducting simulations over a broad range of parameters and configurations. The focus is on adsorbers of larger scale (length L = 0.1 . . . 1 m) and on the discharging process. As the adsorption pair, binderless zeolite 13X with water is examined. The models are developed in a stepwise manner from pore to storage scale. The Finite-Difference-Method is implemented to numerically solve the models. Simulations are conducted for defined reference cases as well as over a broad range of geometric and process parameters. The reference cases are analyzed in detail to gain a better understanding of the transport processes. Furthermore, the results are analyzed with respect to two particular modeling aspects: equilibrium assumptions and rarefaction effects (e. g. slip effect). With respect to the application, the discharging performance is analyzed in terms of thermal power and a defined discharging degree. Both the adsorber and the adsorbent configurations are varied. In addition, the effect of the discharging conditions is evaluated. Finally, one exemplary charging process is examined. The detailed analysis of the reference cases reveals that the mass and heat transport and the adsorption processes are strongly coupled and can only be understood in their interaction. For onedimensional adsorber configurations, that is the mass and heat transport are in the same direction, the discharging process is generally limited by the heat transport. This leads to insufficient thermal power and unsuitable discharging durations of up to one year. In contrast, for two-dimensional adsorber configurations, that is the mass and heat transport are in perpendicular directions, the discharging process can be limited either by the mass or heat transport or by the adsorption. The limitation depends on the configuration of the adsorber and adsorbent. Moreover, the twodimensional adsorber configurations can provide sufficient thermal power. With respect to the modeling, it is found that the assumption of a uniform pressure distribution is applicable for one-dimensional adsorber configurations. In contrast, for two-dimensional configurations, no equilibrium assumptions can be applied in general. However, for powder adsorbent it is always valid to assume local adsorption equilibrium. Regarding the rarefaction effects in twodimensional adsorber configurations with honeycombs and granules, the slip effect is relevant for small channel and particle diameters (d = 1 mm). For adsorbers with powder adsorbent, the reduction of the effective heat conductivity due to the rarefaction effect becomes relevant. With respect to the application, the variation of the adsorber configuration shows that the volumetric thermal power generally decreases with increasing adsorber length. Furthermore, the power decreases with increasing width between the parallel heat exchanger plates in the adsorber. Regarding the adsorbent configuration in two-dimensional adsorber configurations, it is found that the volumetric thermal power can be optimized by variation of the channel or particle diameter. Interestingly, the optima for peak and mean power do not coincide. In addition, the discharging degree is found to strongly depend on the discharging conditions in terms of discharging temperature and volume flow of the heat transfer fluid extracting the heat from the adsorber. In general, the discharging degree decreases with increasing discharging temperature. Similarly, the discharging degree decreases with increasing volume flow of the heat transfer fluid. Finally, the analysis of an exemplary charging process revealed that the pressure in the adsorber can increase significantly (> 50%) due to the desorption.