Universität Stuttgart
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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 Granular architectures : granular materials as "designer matter" in architecture(Stuttgart : Institute for Computational Design and Construction, University of Stuttgart, 2020) Dierichs, Karola; Menges, Achim (Prof.)The thesis investigates designed granular materials in architecture. Granular materials are defined as high numbers of particles larger than a micrometre, between which mainly short-range repulsive contact forces are acting. In a designed granular material the geometry and material of the individual particle are determined by a designer. Consequently, the overall granular material can have characteristics which are novel in comparison to non-designed granular materials. In architecture, designed granular materials are understood to have new characteristics which fulfil specific architectural performance criteria. The relevance of designed granular materials in architecture is threefold. All granular materials are both fully recyclable and reconfigurable due to the fact that the individual particles are in no way bound to each other. These first two aspects alone make any granular material, whether it is designed or not, a highly pertinent strand of architectural design research. However, designed granular materials, in addition to being recyclable and reconfigurable, bear the potential for the development of entirely novel material behaviours. In the context of architecture, designed granular materials can be considered as a form of "material systems", and more specifically as a sub-group of "aggregate systems". In the wider transdisciplinary context, designed granular materials for architecture can be considered a form of "designer matter (DM)". "Designer matter (DM)" is understood as matter which is designed in its structural characteristics at its mesoscale rather than its macro- or its microscale. The current state of research into designed granular materials is presented for both architecture and granular physics, on a conceptual as well as on a project-based level. In this context the thesis aims to establish and validate a first version of a comprehensive design system for exploring designed granular materials in architecture and for interfacing with granular physics. The research development of this thesis is presented and evaluated with respect to the practical, methodological and conceptual foundations which have been laid during this phase. The methods are introduced in terms of methodological frameworks, tools and techniques and the applied research methodology. The core part of the thesis comprises a design system with a related design system catalogue as well as two case studies. The design system is established for particle systems and for related construction systems. It formulates the basic system categories and corresponding parameters. The design system catalogue is presented in the appendix and summarizes tests which investigate individual aspects of the overall design system for particle and construction systems. Each of the two case studies explores the integration of a different set of design system categories. They were conducted both through full-scale prototypes and a related set of tests with statistical repetition. Case study 1 investigates vertical structures made from a designed granular material consisting of highly non-convex particles. Case study 2 combines two designed granular materials, one consisting of convex particles and the other of highly non-convex particles, in order to form spatial enclosures. The case studies are evaluated with respect to their practical, methodological and conceptual contributions to architectural design research. The thesis is summarized and its contributions are assessed in conclusion both with respect to the field of architecture and for the field of granular physics. Further research in the field of designed granular materials in architecture can be conducted on the practical, methodological and conceptual levels of design. On the practical level, in the area of particle systems the investigation of graded granular materials, of different mechanical properties of the particles' material or of designed granular materials consisting of particles with variable geometry is highly promising. In the area of construction systems, the development of behavioural models of robotic construction is very relevant. Another key direction is for the construction systems to become increasingly simple, while the particles are progressively designed to perform parts of the construction process by themselves. On the methodological level, the integration of "inverse" design methods is the logical next step. This can be done on the basis of the proposed design system. On the conceptual level, the framework of "designer matter (DM)" needs to be further established both as a transdisciplinary model and within the field of architecture. Only then can designed granular materials be fully discussed as one form of "designer matter (DM)" in architecture. Key to any further development of the overall research field is the integration of the two fields of architecture and granular physics.Item Open Access Enzymkatalysierte regioselektive N-Methylierung und N-Alkylierung von Pyrazolen(2021) Bengel, Ludwig L.; Hauer, Bernhard (Prof. Dr.)Item Open Access Behavior of concrete structures subjected to static and dynamic loading after fire exposure(2021) Lacković, Luka; Ožbolt, Joško (Prof. Dr.-Ing. habil.)The resistance of concrete structures exposed to extreme loading conditions such as explosion, impact, industrial accidents, tsunami, earthquake or their combination represents one of the major topics in research today. Such loading conditions are characterized with high loading rates often acting in conjunction with fire exposure. Especially vulnerable are the structures located in the seismically active areas with high level of urbanization and proximity to HAZMAT landfills, which additionally exacerbate fire conflagrations. The behavior of concrete changes significantly when exposed to elevated temperatures resulting in the decrease of its mechanical properties. Reinforced concrete (RC), when exposed to high temperature culminates in a simultaneous thermal behavior of its two constituents, steel and concrete, that should be considered in the analysis. It is also known that the resistance, crack pattern and failure mode in concrete are strongly influenced by the loading rate. The dynamic response of RC structures previously exposed to fire changes significantly when compared to initially undamaged RC structures. The main objective of the present work is to further improve the existing rate sensitive thermo-mechanical model for concrete through the following: (i) the implementation of the experimentally obtained thermal dependence of concrete fracture energy in the thermo-mechanical model, (ii) the calculation of concrete thermally dependent mechanical properties by means of nonlocal (average) temperature and (iii) to perform parametric study on fastening elements and RC frames in order to investigate the interaction between the thermally induced damage and mechanical behavior of structures. The experimental investigations in the present work indicated that the concrete fracture energy has a declining tendency with the temperature increase, measured on small and mid-sized concrete beams. This is implemented in the thermo-mechanical model and it is indicated that the decrease of fracture energy has a relatively mild influence on reaction values in terms of loading rate. However, its effect on the fracture patterns and reaction-time histories can be considered as more significant. The influence of the nonlocal temperature is validated against the experimental results carried out on RC frames which had been thermally pre-damaged and subsequently loaded with impact. Currently there are almost no models that can realistically predict the structural behavior at this level of complexity. Furthermore, a parametric study is carried out to show the influence of preloading of single-headed stud anchor and anchor group with two and four studs, on the residual concrete edge failure capacity after fire exposure. The anchors are exposed to fire and loaded in shear, perpendicular to the free edge of the concrete member up to failure, in both hot and cold state (after cooling). The influence of different geometry configurations and initial conditions such as the edge distance, embedment depth, anchor diameter and duration of fire on the load-bearing behavior of anchors is investigated. It is demonstrated that the preloading has a strong negative influence on the residual load-bearing capacity of the concrete. Finally, the numerical parametric study is performed to investigate the influence of fire duration and the loading rate on the resistance of RC frames. The response of the RC structures strongly depends on whether it was loaded in hot or residual (cold) state, i.e. after being naturally cooled down to ambient temperature. Furthermore, an extensive numerical investigation on the influence of post-earthquake fire on the residual capacity of RC frames with and without ductile detailing is conducted. The numerical investigation encompassed the validation of the thermo-mechanical model in terms of temperature distributions, thermal deflections and load-bearing capacity against the test data and subsequent parametric analysis with different levels of fire exposure ranging from 15 to 120 min.