Highly proton conducting polymers for operation in hydrogen/oxygen proton exchange membrane fuel cells (PEMFCs) provide often a poor mechanical strength due to high water contents. To strengthen the conducting polymers, blends with different ratios of partially fluorinated sulfonic acid graft and diblock copolymers with perfluorinated polymers were prepared. To analyze the effect of the different quantities of the compounds, with regard to water sorption and proton conducting properties, membranes were prepared by dissolving the components and drop casting. Partially sulfonated poly([vinylidene difluoride-co-chlorotrifluoroethylene]-g-styrene) (P(VDF-co-CTFE)-g-SPS) was blended with polyvinylidene difluoride (PVDF), decreasing the ion exchange capacity (IEC). The blended polymers absorbed less water. However, the by AC impedance spectroscopy determined proton conductivity stayed stable or increased slightly. The effective proton mobility remained constant. Partially sulfonated poly([vinylidene difluoride-co-hexafluoropropylene]-b-styrene) (P(VDF-co-HFP)-b-SPS) with two different PS-block lengths were blended with different amounts of poly(vinylidene difluoride-co-hexafluoropropylene) (P(VDF-co-HFP)). In that case, the polymers absorbed less water and the proton conductivity decreased stepwise by adding more than 20 wt% P(VDF-co-HFP). The results indicate that a blending of P(VDF-co-CTFE)-g-SPS with PVDF inhibits swelling without having an effect on the proton conductivity, though water sorption and IEC are reduced.

Highly proton conducting polymers for operation in hydrogen/oxygen proton exchange membrane fuel cells (PEMFCs) provide often a poor mechanical strength due to high water contents. To strengthen the conducting polymers, blends with different ratios of partially fluorinated sulfonic acid graft and diblock copolymers with perfluorinated polymers were prepared. To analyze the effect of the different quantities of the compounds, with regard to water sorption and proton conducting properties, membranes were prepared by dissolving the components and drop casting. Partially sulfonated poly([vinylidene difluoride-co-chlorotrifluoroethylene]-g-styrene) (P(VDF-co-CTFE)-g-SPS) was blended with polyvinylidene difluoride (PVDF), decreasing the ion exchange capacity (IEC). The blended polymers absorbed less water. However, the by AC impedance spectroscopy determined proton conductivity stayed stable or increased slightly. The effective proton mobility remained constant. Partially sulfonated poly([vinylidene difluoride-co-hexafluoropropylene]-b-styrene) (P(VDF-co-HFP)-b-SPS) with two different PS-block lengths were blended with different amounts of poly(vinylidene difluoride-co-hexafluoropropylene) (P(VDF-co-HFP)). In that case, the polymers absorbed less water and the proton conductivity decreased stepwise by adding more than 20 wt% P(VDF-co-HFP). The results indicate that a blending of P(VDF-co-CTFE)-g-SPS with PVDF inhibits swelling without having an effect on the proton conductivity, though water sorption and IEC are reduced.:1 Introduction 2 Literature Review 2.1 Fuel Cells 2.1.1 Proton Exchange Membrane Fuel Cells 2.1.2 Other Types of Fuel Cells 2.2 Proton Conductivity 2.3 Proton Conducting Polymers 2.4 Impedance Spectroscopy 2.5 Polymers 2.6 Blending 2.7 Synthesis 2.7.1 Atom Transfer Radical Polymerization 2.7.2 Emulsion Polymerization 3 Results 3.1 Synthesis 3.1.1 Polyvinylidene Diuoride (PVDF) 3.1.2 Diblock Copolymers P(VDF-co-HFP)-b-SPS and Blends 3.1.3 Graft Copolymer P(VDF-co-HFP)-b-SPS Blends 3.2 Degree of Sulfonation 3.3 Ionomer Content 3.4 Ion Exchange Capacity 3.5 Water Content and Uptake 3.6 Proton Concentration 3.7 Watermolecules per Ionic Group 3.8 Proton Conductivity 3.9 Proton Mobility 4 Discussion & Conclusion 5 Experimental Part 5.1 Synthesis 5.1.1 Synthesis of PVDF 5.1.2 Synthesis of P(VDF-co-HFP)-b-PS 5.1.3 Sulfonation of the Polystyrene Block 5.2 Polymer Characterization 5.3 Membrane Preparation 5.4 Membrane Characterization Bibliography Appendix

Advanced monitoring of the spatio-temporal distribution of process parameters in large-scale vessels and containers such as stirred chemical or bioreactors offers a high potential for the investigation and further optimization of plants and embedded processes. This applies especially to large-scale fermentation biogas reactors where the process performance including the biological processes highly depend on mixing parameters of the complex bio-substrates. Sufficient mixing is a basic requirement for a stable operation of the process and adequate process performance. However, this condition is rarely met in agricultural biogas plants and the process efficiency is often reduced dramatically by inhomogeneities in the agitated vessels. Without a doupt, investigation and monitoring of biochemical parameters, such as the fermentation rate, pH distribution as well as O2 and CO2 concentration is of great importance. Nevertheless, also understanding of non-biological parameters, such as fluid dynamics (flow velocity profiles, circulation times), suspension mixing (homogeneity, location of dead zones and short-circuits) and heat transfer (temperature profiles), is necessary to analyze the impact of mixing on the biological system and also to improve the process efficiency. However, in most industrial scale applications the acquisition of these parameters and their spatial distributions in the large-scale vessels is hampered by the limited access to the process itself, because sensor mounting or cable connections are not feasible or desired. Therefore, state of the art instrumentation of such reactors is commonly limited to few spatial positions where it is doubtfully assumed that the measured parameters are representative for the whole reaction mixture. In this work, a concept of flow following sensor particles was developed. The sensor particles allow long-term measurement of spatially distributed process parameters in the chemically and mechanically harsh environments of agitated industrial vessels. Each sensor particle comprises of an onboard measurement electronics that logs the signals of measurement devices, namely temperature, absolute pressure (immersion depth, axial position) and 3D acceleration. The whole electronics is enclosed in a robust neutrally buoyant capsule (equivalent diameter 58.2 mm; sphericity 0.91), to allow free movement with the flow. The sensor particles were tested in pilot fermenters under comparable flow conditions of biogas fermenters. The experiments proved the applicability of the sensor particles and the robustness to resist the harsh environments of mixing processes. Moreover, the results show the capabilities of the sensor particles to monitor the internal conditions of the vessel correctly and thus deliver significant information about the flow regime. Therefore effects of liquid rheology, vessel geometry, impeller speed and axial impeller position on the macro-mixing process were properly detected. Evaluation of the impeller efficiency and the mixing processes was done based on mixing homogeneity, location of dead zones, axial velocity profiles, circulation time distributions as well as average circulation times, acceleration spectra and temperature profiles that were extracted from the measured data. Furthermore, it is shown, that parameters of mixing models such as circulation number, impeller head, PECLÉT-number and variance of suspended solid particles can be estimated from the measured data. The main achievement of this work is therefore the development and validation of instrumented flow followers for the investigation of macro-mixing effects in agitated vessels. The sensor particles show potential for employment to real applications such as biogas fermenters or large bioreactors and to monitor and improve the mixing and heating regimes.

Advanced monitoring of the spatio-temporal distribution of process parameters in large-scale vessels and containers such as stirred chemical or bioreactors offers a high potential for the investigation and further optimization of plants and embedded processes. This applies especially to large-scale fermentation biogas reactors where the process performance including the biological processes highly depend on mixing parameters of the complex bio-substrates. Sufficient mixing is a basic requirement for a stable operation of the process and adequate process performance. However, this condition is rarely met in agricultural biogas plants and the process efficiency is often reduced dramatically by inhomogeneities in the agitated vessels. Without a doupt, investigation and monitoring of biochemical parameters, such as the fermentation rate, pH distribution as well as O2 and CO2 concentration is of great importance. Nevertheless, also understanding of non-biological parameters, such as fluid dynamics (flow velocity profiles, circulation times), suspension mixing (homogeneity, location of dead zones and short-circuits) and heat transfer (temperature profiles), is necessary to analyze the impact of mixing on the biological system and also to improve the process efficiency. However, in most industrial scale applications the acquisition of these parameters and their spatial distributions in the large-scale vessels is hampered by the limited access to the process itself, because sensor mounting or cable connections are not feasible or desired. Therefore, state of the art instrumentation of such reactors is commonly limited to few spatial positions where it is doubtfully assumed that the measured parameters are representative for the whole reaction mixture. In this work, a concept of flow following sensor particles was developed. The sensor particles allow long-term measurement of spatially distributed process parameters in the chemically and mechanically harsh environments of agitated industrial vessels. Each sensor particle comprises of an onboard measurement electronics that logs the signals of measurement devices, namely temperature, absolute pressure (immersion depth, axial position) and 3D acceleration. The whole electronics is enclosed in a robust neutrally buoyant capsule (equivalent diameter 58.2 mm; sphericity 0.91), to allow free movement with the flow. The sensor particles were tested in pilot fermenters under comparable flow conditions of biogas fermenters. The experiments proved the applicability of the sensor particles and the robustness to resist the harsh environments of mixing processes. Moreover, the results show the capabilities of the sensor particles to monitor the internal conditions of the vessel correctly and thus deliver significant information about the flow regime. Therefore effects of liquid rheology, vessel geometry, impeller speed and axial impeller position on the macro-mixing process were properly detected. Evaluation of the impeller efficiency and the mixing processes was done based on mixing homogeneity, location of dead zones, axial velocity profiles, circulation time distributions as well as average circulation times, acceleration spectra and temperature profiles that were extracted from the measured data. Furthermore, it is shown, that parameters of mixing models such as circulation number, impeller head, PECLÉT-number and variance of suspended solid particles can be estimated from the measured data. The main achievement of this work is therefore the development and validation of instrumented flow followers for the investigation of macro-mixing effects in agitated vessels. The sensor particles show potential for employment to real applications such as biogas fermenters or large bioreactors and to monitor and improve the mixing and heating regimes.