The horizontal twin-roll casting (TRC) process is an energy saving and cost-efficient method for producing near-net-shape sheets of castable metals for light-weight production. In order to investigate the TRC process numerically, a code is generated in OpenFOAM and the commercial software STAR-CCM+ is used. Both are validated with the Stefan problem, the gallium melting test case, and a continuous casting experiment for magnesium AZ31. Different solidification models are tested that are similar to solution domain definitions and solid-fraction temperature relations. The comparison with temperature measurements of the MgF GmbH Freiberg pilot plant and the final microstructure exhibits good correlation. Sensitivity studies are carried out for thermophysical properties of AZ31 as well as pilot plant parameters. Furthermore, the rolls are incorporated into the simulation to determine the effect of a location-dependent heat-transfer coefficient. Finally, the results are compared to a second pilot plant situated at the Helmholtz-Centre Geesthacht in order to explore differences and similarities. / Das horizontales Gießwalzen ist eine energiesparende und kostengünstige Methode zur Erzeugung von Flachprodukten, die im Leichtbau verwendet werden. Um dieses Verfahren numerisch zu untersuchen wurde ein Programmcode in OpenFOAM entwickelt und die kommerzielle Software STAR-CCM+ verwendet, wobei beide mit dem Stefan Problem, dem Schmelzen von Gallium und Messdaten des Stranggusses von Magnesium AZ31 validiert wurden. Verschiedene Erstarrungsmodelle werden ebenso getestet wie Variationen des Simulationsbereiches und Feststoff-Temperatur-Verläufe. Vergleiche mit Temperaturmessdaten der Pilotanlage MgF GmbH Freiberg und der finalen Mikrostruktur zeigen gute Übereinstimmungen. Sensitivitätsanalysen werden durchgeführt, um die Einflüsse von thermophysikalischen Eigenschaften und Anlagenparametern abzuschätzen. Des Weiteren werden die Walzen in die Simulation mit einbezogen, um den Effekt eines lokal veränderlichen Wärmeübergangskoeffizienten zu beurteilen. Schließlich werden die Ergebnisse mit denen einer zweiten Pilotanlage am Helmholtz-Zentrum Geesthacht verglichen. / Le laminage de coulée continue horizontal possède une faible consommation d’énergie et est bon marché pour la production des feuilles de métaux coulables utilisés dans la construction légère. Afin d’examiner ce processus numériquement, un code est généré dans OpenFOAM et le logiciel commercial STAR-CCM+ est utilisé, tous les deux sont validés en utilisant le problème de Stefan, la fusion du gallium et la coulée continue verticale de magnésium AZ31. Plusieurs modèles de solidification sont testés, ainsi que la variation du domaine de simulation, et des rélations entre la teneur en matière solide et la température. Des comparaisons avec des résultats de mesures de la température à l’installation pilote de MgF GmbH Freiberg ainsi que la microstructure donnent des bons résultats. Des analyses de sensibilité sont effectuées afin d’évaluer l’influence des propriétés thermophysiques et des paramètres de l’installation. De plus, les cylindres sont intégrés dans la simulation pour estimer l’impact du coefficient de transfert de chaleur dépendant du lieu. Finalement, les résultats sont comparés avec ceux du Helmholtz-Centre Geesthacht.

The rapidly increasing power conversion efficiencies (PCEs) of organic solar cells (OSCs) above 10% were made possible by concerted international research activities in the last few years, aiming to understand the processes that lead to the generation of free charge carriers following photon absorption. Despite these efforts, many details are still unknown, especially how these processes can be improved already at the drawing board of molecular design. To unveil this information, dicyanovinyl end-capped oligothiophene derivatives (DCVnTs) are used as a model system in this thesis, allowing to investigate the impact of small structural changes on the molecular properties and the final solar cells. On thin films of a methylated DCV4T derivative, the influence of the measurement temperature on the charge carrier generation process is investigated. The observed temperature activation in photoinduced absorption (PIA) measurements is attributed to an increased charge carrier mobility, increasing the distance between the charges at the donor/acceptor (D/A) interface and, thus, facilitating their final dissociation. The correlation between the activation energy and the mobility is confirmed using a DCV6T derivative with lower mobility , exhibiting a higher activation energy for charge carrier generation. Another parameter to influence the charge carrier generation process is the molecular structure. Here, alkyl side chains with varying length are introduced and their influence on the intramolecular energy levels as well as the absorption and emission properties in pristine and blend films with the acceptor C60 are examined. The observed differences in intermolecular order (higher order for shorter side chains) and phase separation in blend layers (larger phase separation for shorter side chains) are confirmed in PIA measurements upon comparing the temperature dependence of the triplet exciton lifetimes. A proposed correlation between the side chain length and the coupling between D and A, which is crucial for efficient charge transfer, is not confirmed. The presented flat heterojunction solar cells underline this conclusion, giving similar photocurrent densities for all compounds. Differences in PCE are related to shifts of the energy levels and the morphology of the blend layer in bulk heterojunction devices. Furthermore, the impact of the electric field on the charge carrier generation yield is investigated in a proof-of-principle study, introducing PIA measurements in transmission geometry realized using semitransparent solar cells. The recombination analysis of the photogenerated charge carriers reveals two recombination components. Trapped charge carriers or bound charge pairs at the D/A interface are proposed as an explanation for this result. The miscibility of D and A, which can be influenced by heating the substrate during layer deposition, is of crucial importance to obtain high PCEs. In this work, the unusual negative influence of the substrate temperature on DCV4T:C60 blend layers in solar cells is investigated. By using optical measurements and structure determination tools, a rearrangement of the DCV4T crystallites is found to be responsible for the reduced absorption and, therefore, photocurrent at higher substrate temperature. The proposed blend morphology at a substrate temperature of 90° C is characterized by a nearly complete demixing of the D and A phases. This investigation is of particular relevance, because it shows the microscopic origins of a behavior that is contrary to the increase of the PCE upon substrate heating usually reported in literature. Finally, the optimization steps to achieve a record PCE of 7.7% using a DCV5T derivative as donor material are presented, including the optimization of the substrate temperature, the active layer thickness, and the transport layers.:Abstract - Kurzfassung Publications Contents 1 Introduction 2 Elementary Processes in Organic Semiconductors 2.1 Introduction 2.2 Optical Excitations in Organic Materials 2.2.1 Introduction 2.2.2 Radiative Processes: Absorption and Emission 2.2.3 Non-radiative Relaxation Processes 2.2.4 Triplet Excitons and Intersystem Crossing 2.3 Polarization Effects and Disorder 2.4 Transport Processes in Disordered Organic Materials 2.4.1 Charge Transport 2.4.1.1 The Bässler Model 2.4.1.2 Marcus Theory for Electron Transfer 2.4.1.3 Small Polaron Model 2.4.1.4 Functional Dependencies of the Charge Carrier Mobility 2.4.2 Diffusive Motion 2.4.3 Exciton Transfer Mechanisms 2.4.4 Characteristics of Exciton Diffusion 2.5 Charge Photogeneration in Pristine Materials 3 Organic Photovoltaics 3.1 General Introduction to Solar Cell Physics 3.2 Introduction to the Donor/Acceptor Heterojunction Concept 3.3 The Open-Circuit Voltage in Organic Solar Cells 3.4 Doping of Organic Semiconductors 3.5 Introduction to the p-i-n Concept 3.6 Charge Transfer Excitons in Donor/Acceptor Heterojunction Systems 3.6.1 Introduction 3.6.2 Verification of Charge Transfer Excitons in Donor/Acceptor Systems 3.7 The Process Cascade for Free Charge Carrier Generation in Donor/Acceptor Heterojunction Systems 3.7.1 The Initial Charge Transfer Step 3.7.2 The Binding Energy of the Charge Transfer Exciton 3.7.3 \"Hot\" Charge Transfer Exciton Dissociation 3.7.4 \"Cold\" Charge Transfer Exciton Dissociation 3.7.5 Supposed Influence Factors on Charge Transfer Exciton Dissociation 3.7.6 Recombination Pathways for Charge Transfer Excitons 3.7.7 Free Charge Carrier Formation and Recombination 4 Experimental Methods 4.1 Sample Preparation 4.2 Material Characterization Methods 4.2.1 Optical Characterization 4.2.2 Cyclic Voltammetry 4.2.3 Ultraviolet Photoelectron Spectroscopy 4.2.4 Atomic Force Microscopy 4.2.5 Grazing Incidence X-Ray Diffraction 4.2.6 Organic Field-Effect Transistor 4.3 Photoinduced Absorption Spectroscopy 4.3.1 Introduction 4.3.2 Derivation of the PIA Signal 4.3.3 Recombination Dynamics 4.3.4 Intensity Dependence of the PIA Signal 4.4 Solar Cell Characterization 4.4.1 External Quantum Efficiency 4.4.2 Spectral Mismatch Correction 4.4.3 Current-Voltage Characteristics 4.4.4 Optical Device Simulations 4.4.5 Optical Device Transmission Measurements 5 The Oligothiophene Material System 5.1 Introduction 5.2 Thermal Stability 5.3 Energy Levels 5.4 Optical Properties of the Pristine Materials 5.5 The Donor/Acceptor Couple: DCVnT and C60 5.6 Solar Cell Devices 5.7 Summary 6 Temperature Dependence of Charge Carrier Generation 6.1 Introduction 6.2 Principal Introduction to the PIA Measurements 6.2.1 Interpretation of the Spectra 6.2.2 Interpretation of the Frequency Scans 6.3 Temperature Dependence of the Spectra 6.4 Discussion of the Temperature Dependent Processes in the Blend Layer 6.5 Temperature Activated Free Charge Carrier Generation 6.5.1 Evaluation of the Activation Energy for the DCV4T-Me:C60 Blend 6.5.2 Comparison to a Sexithiophene Derivative (DCV6T-Me) 6.6 Summary 7 Side Chain Investigation on Quaterthiophene Derivatives 7.1 Energy Levels 7.2 Optical Properties 7.2.1 Solution and Pristine Films 7.2.2 Mixed Films with C60 7.3 Influence of the Side Chain Length on the Intermolecular Coupling 7.3.1 PIA Spectra of Pristine and Blend Layers at 10K 7.3.2 Recombination Analysis for Pristine and Blend Films at 10K 7.4 The Influence of the Side Chain Length on the Offset Charge Carrier Generation Rate at Low Temperature 7.5 In the High-Temperature Limit: Implications for Solar Cell Devices 7.5.1 PIA Spectra in Pristine and Blend Films at 200K 7.5.2 Recombination Analysis: Triplet Excitons and Free Charge Carriers 7.6 Solar Cells 7.6.1 Flat Heterojunction Devices 7.6.2 Bulk Heterojunction Devices 7.7 Summary 8 Electric-Field Dependent PIA Measurements on Complete Solar Cell Devices 8.1 Introduction 8.2 Semitransparent Organic Solar Cells 8.3 Photoinduced Absorption Measurements 8.4 Summary and Outlook 9 The Effect of Substrate Heating During Layer Deposition on the Performance of DCV4T:C60 BHJ Solar Cells 9.1 Introduction 9.2 The Importance of Morphology Control for BHJ Solar Cells 9.3 The Impact of Substrate Heating on DCV4T:C60 BHJ Solar Cells 9.4 Absorption and Photoluminescence 9.5 Topographical Investigations (AFM) 9.6 X-ray Investigations 9.6.1 1D GIXRD Measurements 9.6.2 2D GIXRD Measurements 9.7 Proposed Morphological Picture and Confirmation Measurements 9.7.1 Morphology Sketch of the DCV4T:C60 Blend Layer 9.7.2 Confirmation Measurements 9.8 The Equivalence of Temperature and Time 9.9 Summary 10 Record Solar Cells Using DCV5T-Me33 as Donor Material 10.1 Introduction 10.2 The Influence of the Substrate Temperature 10.3 Determination of the Optical Constants 10.4 Stack Optimization 10.5 Summary and Outlook 11 Conclusions and Outlook 11.1 Summary of the Photophysical Investigations 11.2 Summary of Device Investigations 11.3 Future Challenges Appendix A Detailed Description of the Experimental Setup for PIA Spectroscopy Appendix B Determination of the Triplet Level by Differential PL Measurements Appendix C Additional Tables and Figures Appendix D Reproducibility of the Solar Cell Results (Statistics) Appendix E Lists Bibliography Acknowledgments / Der rasante Anstieg des Wirkungsgrads von organischen Solarzellen über die Marke von 10% war nur durch länderübergreifende Forschungsaktivitäten während der letzten Jahre möglich. Trotz der gemeinsamen Anstrengungen, die Prozesse, die zwischen der Absorption der Photonen und der Ladungsträgererzeugung liegen, genauer zu verstehen, sind einige Fragen jedoch immer noch ungelöst, z.B. wie diese Prozesse schon auf dem Reißbrett durch die gezielte Änderung bestimmter Molekülstrukturen optimiert werden können. Um dieses Ziel zu erreichen, werden in dieser Arbeit Dicyanovinyl-substituierte Oligothiophene (DCVnTs) verwendet. Diese Materialien bieten die Möglichkeit, kleine strukturelle Änderungen vorzunehmen, deren Einfluss auf die molekularen und auf die Solarzelleneigenschaften untersucht werden soll. Der Einfluss der Messtemperatur auf den Prozess der Ladungsträgertrennung wird hier an einer methylierten DCV4T-Verbindung in einer dünnen Schicht untersucht. Die bei photoinduzierter Absorptionsspektroskopie (PIA) beobachtete Aktivierung dieses Prozesses mit zunehmender Temperatur wird auf eine erhöhte Ladungsträgerbeweglichkeit zurückgeführt. Der dadurch erhöhte effektive Abstand der Ladungen an der Grenzfläche zwischen Donator (D) und Akzeptor (A) erleichtert die endgültige Trennung der Ladungsträger. Durch den Vergleich mit einer DCV6T-Verbindung wird der Zusammenhang zwischen der Aktivierungsenergie und der Beweglichkeit bekräftigt. Die kleinere Beweglichkeit äußert sich dabei in einer größeren Aktivierungsenergie. Darüber hinaus kann der Ladungsträgergenerationsprozess auch von der Molekülstruktur abhängen. In dieser Arbeit wird untersucht, wie sich die Länge von Alkylseitenketten auf die Energieniveaus der Moleküle, aber auch auf die Absorptions- und Lumineszenzeigenschaften der Materialien in reinen und in Mischschichten mit dem Akzeptor C60 äußert. Die ermittelten Unterschiede bezüglich der Molekülordnung (geordneter für kürzere Seitenketten) und der Phasengrößen in Mischschichten (größere Phasen bei kürzerer Kettenlänge) werden in der Untersuchung der Temperaturabhängigkeit der Lebensdauer von Triplettexzitonen mittels PIA-Messungen bestätigt. Für Solarzellen ist von Bedeutung, ob sich die Seitenkettenlänge auf die Wechselwirkung zwischen D und A auswirkt. Der vermutete Zusammenhang wird hier nicht bestätigt. Ein ähnlicher Photostrom für alle untersuchten Verbindungen in Solarzellen mit planaren Heteroübergängen unterstreicht diese Schlussfolgerung. Unterschiede im Wirkungsgrad werden auf Änderungen der Energieniveaus und die Morphologie in Mischschichtsolarzellen zurückgeführt. Des Weiteren wird in einer Machbarkeitsstudie der Einfluss des elektrischen Felds auf die Generationsausbeute freier Ladungsträger untersucht. Dafür werden halbtransparente Solarzellen verwendet, die es ermöglichen, PIA-Messungen in Transmissionsgeometrie durchzuführen. Als mögliche Erklärung für das Auftreten zweier Rekombinationskomponenten in der Analyse des Rekombinationsverhaltens der durch Licht erzeugten Ladungsträger werden eingefangene Ladungsträger und gebundene Ladungsträgerpaare an der D/A-Grenzfläche genannt. Das Mischverhalten von D und A kann durch ein Heizen des Substrates während des Verdampfungsprozesses eingestellt werden, was von entscheidender Bedeutung für eine weitere Steigerung des Wirkungsgrades ist. Für DCV4T:C60-Mischschichtsolarzellen wird jedoch eine Verschlechterung des Wirkungsgrads zu höheren Substrattemperaturen beobachtet. Durch optische Messungen und Methoden zur Schichtstrukturbestimmung wird dieser Effekt auf eine Umordnung der DCV4T-Kristallite für hohe Substrattemperaturen und die damit verbundene Verringerung der Absorption und damit auch des Photostroms zurückgeführt. Bei einer Substrattemperatur von 90° C sind die D- und A-Komponenten fast vollständig entmischt. Dieses Beispiel ist von besonderer Bedeutung, weil hier die Ursachen für ein Verhalten aufgezeigt werden, das entgegen den Beispielen aus der Literatur eine Abnahme des Wirkungsgrads beim Aufdampfen der aktiven Schicht auf ein geheiztes Substrat zeigt. Schließlich werden die Optimierungsschritte dargelegt, mit denen Solarzellen mit einer DCV5T-Verbindung als Donatormaterial auf einen Rekordwirkungsgrad von 7,7% gebracht werden. Dabei wird die Substrattemperatur, die Dicke der aktiven Schicht und die Transportschichten angepasst.:Abstract - Kurzfassung Publications Contents 1 Introduction 2 Elementary Processes in Organic Semiconductors 2.1 Introduction 2.2 Optical Excitations in Organic Materials 2.2.1 Introduction 2.2.2 Radiative Processes: Absorption and Emission 2.2.3 Non-radiative Relaxation Processes 2.2.4 Triplet Excitons and Intersystem Crossing 2.3 Polarization Effects and Disorder 2.4 Transport Processes in Disordered Organic Materials 2.4.1 Charge Transport 2.4.1.1 The Bässler Model 2.4.1.2 Marcus Theory for Electron Transfer 2.4.1.3 Small Polaron Model 2.4.1.4 Functional Dependencies of the Charge Carrier Mobility 2.4.2 Diffusive Motion 2.4.3 Exciton Transfer Mechanisms 2.4.4 Characteristics of Exciton Diffusion 2.5 Charge Photogeneration in Pristine Materials 3 Organic Photovoltaics 3.1 General Introduction to Solar Cell Physics 3.2 Introduction to the Donor/Acceptor Heterojunction Concept 3.3 The Open-Circuit Voltage in Organic Solar Cells 3.4 Doping of Organic Semiconductors 3.5 Introduction to the p-i-n Concept 3.6 Charge Transfer Excitons in Donor/Acceptor Heterojunction Systems 3.6.1 Introduction 3.6.2 Verification of Charge Transfer Excitons in Donor/Acceptor Systems 3.7 The Process Cascade for Free Charge Carrier Generation in Donor/Acceptor Heterojunction Systems 3.7.1 The Initial Charge Transfer Step 3.7.2 The Binding Energy of the Charge Transfer Exciton 3.7.3 \"Hot\" Charge Transfer Exciton Dissociation 3.7.4 \"Cold\" Charge Transfer Exciton Dissociation 3.7.5 Supposed Influence Factors on Charge Transfer Exciton Dissociation 3.7.6 Recombination Pathways for Charge Transfer Excitons 3.7.7 Free Charge Carrier Formation and Recombination 4 Experimental Methods 4.1 Sample Preparation 4.2 Material Characterization Methods 4.2.1 Optical Characterization 4.2.2 Cyclic Voltammetry 4.2.3 Ultraviolet Photoelectron Spectroscopy 4.2.4 Atomic Force Microscopy 4.2.5 Grazing Incidence X-Ray Diffraction 4.2.6 Organic Field-Effect Transistor 4.3 Photoinduced Absorption Spectroscopy 4.3.1 Introduction 4.3.2 Derivation of the PIA Signal 4.3.3 Recombination Dynamics 4.3.4 Intensity Dependence of the PIA Signal 4.4 Solar Cell Characterization 4.4.1 External Quantum Efficiency 4.4.2 Spectral Mismatch Correction 4.4.3 Current-Voltage Characteristics 4.4.4 Optical Device Simulations 4.4.5 Optical Device Transmission Measurements 5 The Oligothiophene Material System 5.1 Introduction 5.2 Thermal Stability 5.3 Energy Levels 5.4 Optical Properties of the Pristine Materials 5.5 The Donor/Acceptor Couple: DCVnT and C60 5.6 Solar Cell Devices 5.7 Summary 6 Temperature Dependence of Charge Carrier Generation 6.1 Introduction 6.2 Principal Introduction to the PIA Measurements 6.2.1 Interpretation of the Spectra 6.2.2 Interpretation of the Frequency Scans 6.3 Temperature Dependence of the Spectra 6.4 Discussion of the Temperature Dependent Processes in the Blend Layer 6.5 Temperature Activated Free Charge Carrier Generation 6.5.1 Evaluation of the Activation Energy for the DCV4T-Me:C60 Blend 6.5.2 Comparison to a Sexithiophene Derivative (DCV6T-Me) 6.6 Summary 7 Side Chain Investigation on Quaterthiophene Derivatives 7.1 Energy Levels 7.2 Optical Properties 7.2.1 Solution and Pristine Films 7.2.2 Mixed Films with C60 7.3 Influence of the Side Chain Length on the Intermolecular Coupling 7.3.1 PIA Spectra of Pristine and Blend Layers at 10K 7.3.2 Recombination Analysis for Pristine and Blend Films at 10K 7.4 The Influence of the Side Chain Length on the Offset Charge Carrier Generation Rate at Low Temperature 7.5 In the High-Temperature Limit: Implications for Solar Cell Devices 7.5.1 PIA Spectra in Pristine and Blend Films at 200K 7.5.2 Recombination Analysis: Triplet Excitons and Free Charge Carriers 7.6 Solar Cells 7.6.1 Flat Heterojunction Devices 7.6.2 Bulk Heterojunction Devices 7.7 Summary 8 Electric-Field Dependent PIA Measurements on Complete Solar Cell Devices 8.1 Introduction 8.2 Semitransparent Organic Solar Cells 8.3 Photoinduced Absorption Measurements 8.4 Summary and Outlook 9 The Effect of Substrate Heating During Layer Deposition on the Performance of DCV4T:C60 BHJ Solar Cells 9.1 Introduction 9.2 The Importance of Morphology Control for BHJ Solar Cells 9.3 The Impact of Substrate Heating on DCV4T:C60 BHJ Solar Cells 9.4 Absorption and Photoluminescence 9.5 Topographical Investigations (AFM) 9.6 X-ray Investigations 9.6.1 1D GIXRD Measurements 9.6.2 2D GIXRD Measurements 9.7 Proposed Morphological Picture and Confirmation Measurements 9.7.1 Morphology Sketch of the DCV4T:C60 Blend Layer 9.7.2 Confirmation Measurements 9.8 The Equivalence of Temperature and Time 9.9 Summary 10 Record Solar Cells Using DCV5T-Me33 as Donor Material 10.1 Introduction 10.2 The Influence of the Substrate Temperature 10.3 Determination of the Optical Constants 10.4 Stack Optimization 10.5 Summary and Outlook 11 Conclusions and Outlook 11.1 Summary of the Photophysical Investigations 11.2 Summary of Device Investigations 11.3 Future Challenges Appendix A Detailed Description of the Experimental Setup for PIA Spectroscopy Appendix B Determination of the Triplet Level by Differential PL Measurements Appendix C Additional Tables and Figures Appendix D Reproducibility of the Solar Cell Results (Statistics) Appendix E Lists Bibliography Acknowledgments

Die vorliegende Arbeit liefert einen Beitrag zum Verständnis der elektrochemischen Prozesse an der Elektrodengrenzfläche und im Festkörper graphitischer Anoden für Lithium-Ionen-Batterien. Der Zusammenhang zwischen den intrinsischen Eigenschaften des Aktivmaterials und den resultierenden Eigenschaften von Kompositelektroden stand dabei im Fokus der Untersuchungen. Die Temperaturabhängigkeit von Materialeigenschaften (Diffusionskoeffizient, Austauschstromdichte) und Elektrodeneigenschaften (Verhalten unter Strombelastung) wurde in einem Bereich von 40 °C bis -10 °C erfasst. Dazu werden elektrochemische Charakterisierungsmethoden aus der Literatur vorgestellt und hinsichtlich ihrer Gültigkeit für die Anwendung an realen Elektroden evaluiert. Die elektrochemisch aktive Oberfläche wurde bestimmt und stellte sich als ausschlaggebender Parameter für die Bewertung der Elektrodenprozesse heraus. Auf Basis korrigierter Elektrodenoberflächen konnten Austauschstromdichten für die konkurrierenden Prozesse Lithium-Interkalation und -Abscheidung ermittelt werden. Zusammen mit Kennwerten zur Keimbildungsüberspannung für Lithium-Abscheidung flossen die ermittelten Kennwerte in eine theoretische Berechnung des Zellstroms ein. Es konnte gezeigt werden, dass die Lithium-Abscheidung kinetisch deutlich gegenüber der Lithium-Interkalation bevorzugt ist, nicht nur bei niedriger Temperatur. Die Übertragbarkeit wissenschaftlicher Grundlagenexperimente auf kommerzielle Systeme war bei allen Versuchen Gegenstand der Untersuchungen. In einem separaten Beispiel einer Oberflächenmodifikation mit Zinn wurde diese Problematik besonders verdeutlicht. Zusätzlich wurde die parasitäre Abscheidung von Lithium auf graphitischen Anoden hinsichtlich der Nachweisbarkeit und Quantifizierung evaluiert. Hierfür wurde eine neue Untersuchungsmethode im Bereich der Lithium-Ionen-Batterie zur besseren Detektion von Lithium-Abscheidung und Grenzflächen-Morphologie mittels Elektronenmikroskopie entwickelt. Die Osmiumtetroxid (OsO4) Färbung ermöglichte eine deutliche Verbesserung des Materialkontrasts und erlaubte somit eine gezielte Untersuchung von graphitischen Anoden nach erfolgter Lithium-Abscheidung. Darüber hinaus konnte die selektive Reaktion des OsO4 für eine genauere Betrachtung der Solid Electrolyte Interphase genutzt werden. Eine Stabilisierung der Proben an Luft und im Elektronenstrahl konnte erreicht werden. / This work sheds light on the electrochemical processes occurring at commercially processed graphitic anodes. It raises the question whether values published in literature for mostly ideal electrode systems can be readily taken for simulation and design of real electrodes in high-energy cells. A multiple step approach is given, evaluating different methods to determine electrode and material properties independently. The electrochemically active surface area was shown to be a crucial parameter for the calculation of electrode kinetics. Using exchange current densities corrected for the electrode surface area, the overall charging current in a cell could be calculated. The resulting part of lithium deposition in the charging process is strikingly high, not only at low temperatures. To further investigate lithium deposition in terms of morphology and quantity, a method was developed for graphitic anodes. Osmium tetroxide (OsO4) staining serves well as a tool to strongly increase material contrast in electron microscopy. Thus lithium dendrites could be made visible in an unprecedented manner. Furthermore, the selective chemical reaction of osmium tetroxide allows for a better investigation of the multi-layer solid electrolyte interphase as was shown in transmission electron microscopy. Using the staining method, a stabilization of the sample under air and in the electron beam could be achieved.

Trace component analysis in gasification processes are important part of elemental component balances in order to understand the fate of these participating compounds in the feedstock. Residual traces in the raw synthesis gas after quench could bring about the poisoning of catalysts and corrosion effects on plant facilities. The objective of this work is to investigate the effects of quenching operation on the trace components during test campaigns of the autothermal non-catalytic reforming of natural gas (Gas-POX) mode in the HP POX (high pressure partial oxidation) test plant. In order to achieve this, Aspen Plus simulation model of the quench chamber of the HP POX test plant was developed to re-calculate the quench chamber input amount of different trace compounds from their output amount measured during test points of the Gas-POX campaigns. Variation in quench water temperatures from 130 °C to 220 °C and pH value of quench water as well as the resulting variation in Henry´s and Dissociation constant of the traces (CO2, H2S, NH3 and HCN) changed the distribution of traces calculated in the quench water. The formation of traces of organic acid (formic acid and acetic acid) and traces of BTEX, PAHs and soot in the quench water effluent were discussed. The discrepancies between equilibrium constant and reaction quotient (non-equilibrium or real) for the formation of NH3 and HCN at the exit of the gasifier were discussed. The assessment of the results in this work should lead to the improvement in the understanding of trace components and concepts that could be employed to influence their formation and reduction.

Trace component analysis in gasification processes are important part of elemental component balances in order to understand the fate of these participating compounds in the feedstock. Residual traces in the raw synthesis gas after quench could bring about the poisoning of catalysts and corrosion effects on plant facilities. The objective of this work is to investigate the effects of quenching operation on the trace components during test campaigns of the autothermal non-catalytic reforming of natural gas (Gas-POX) mode in the HP POX (high pressure partial oxidation) test plant. In order to achieve this, Aspen Plus simulation model of the quench chamber of the HP POX test plant was developed to re-calculate the quench chamber input amount of different trace compounds from their output amount measured during test points of the Gas-POX campaigns. Variation in quench water temperatures from 130 °C to 220 °C and pH value of quench water as well as the resulting variation in Henry´s and Dissociation constant of the traces (CO2, H2S, NH3 and HCN) changed the distribution of traces calculated in the quench water. The formation of traces of organic acid (formic acid and acetic acid) and traces of BTEX, PAHs and soot in the quench water effluent were discussed. The discrepancies between equilibrium constant and reaction quotient (non-equilibrium or real) for the formation of NH3 and HCN at the exit of the gasifier were discussed. The assessment of the results in this work should lead to the improvement in the understanding of trace components and concepts that could be employed to influence their formation and reduction.:List of Figures vii List of Tables xii List of Abbreviations and Symbols xiii 1 Introduction 1 1.1 Background 1 1.2 Objective of the Work 4 1.3 Overview of the Work 5 2 Process and test conditions 6 2.1 HP POX test plant 6 2.2 Test campaign procedure 8 2.2.1 Gas-POX operating parameter range 8 2.2.2 Gas-POX experiments 9 2.2.3 Net reactions of partial oxidation 9 2.3 Gaseous feedstock characterization 11 2.3.1 Natural gas feedstock composition 11 2.4 Analytical methods for gaseous products 12 2.4.1 Hot gas sampling 12 2.4.2 Raw synthesis gas analysis after quench 13 2.5 Aqueous phase product analysis 14 2.5.1 Molecularly dissolved trace compounds and their ions trace analysis 14 2.5.2 Other trace analysis 15 2.6 Limit of accuracy in measurement systems 15 2.7 Summary 17 3 Simulation and methods 18 3.1 Test points calculation of the HP POX test campaign 18 3.1.1 Aspen Plus model for HP POX quench water system 19 3.2 Gas-POX 201 VP1 quench water system model simulation by Aspen Plus 23 3.2.1 Measured and calculated input parameters 23 3.2.2 Calculated sensitivity studies of species and their distribution for test point (VP1) 24 3.3 Used calculation tools related to the work 25 3.3.1 VBA in Excel 25 3.3.2 Python as interface between Aspen Plus and Microsoft Excel 26 3.3.3 Aspen Simulation Workbook 27 3.4 Summary 29 4 Trace components in quench water system 30 4.1 Physico-chemical parameters of quench water 31 4.1.1 Quench water pH adjustment 32 4.1.2 Henry constant 34 4.1.3 Dissociation constant 35 4.1.4 Organic acids in quench water 38 4.2 Carbon dioxide (CO2) 39 4.2.1 Results of sensitivity study: quench water temperature variation effects on CO2 41 4.2.2 Results of sensitivity study: quench water pH variation influence on CO2 42 4.3 Nitrogen compounds 43 4.3.1 Ammonia (NH3) 44 4.3.2 Results of sensitivity study: quench water temperature variation effects on NH3 46 4.3.3 Results of sensitivity study: quench water pH variation influence on NH3 47 4.3.4 Hydrogen Cyanide (HCN) 48 4.3.5 Results of sensitivity study: quench water temperature variation effects on HCN 50 4.3.6 Results of sensitivity study: quench water pH variation influence on HCN 50 4.4 Sulphur compounds: H2S 51 4.4.1 Results of sensitivity study: quench water temperature variation effects on H2S 53 4.4.2 Results of sensitivity study: quench water pH variation influence on H2S 54 4.5 Summary 55 5 Organic acids trace studies in quench water 57 5.1 Organic acids interaction with ammonia compounds in the quench water 57 5.2 Formic acid 62 5.2.1 Trace of formic acid in quench water 64 5.3 Acetic acid 67 5.3.1 Trace of acetic acid in quench water 69 5.4 Summary 72 6 Temperature approach studies for NH3 and HCN formation in gasifier 74 6.1 Nitrogen compounds: NH3 and HCN 74 6.2 Ammonia (NH3) formation in the gasifer 77 6.3 Hydrogen cyanide (HCN) formation in the gasifier 79 6.4 Discrepancies between back-calculated reaction quotients and equilibrium constants of the NH3 formation 81 6.4.1 Case 1: calculated equilibrium distribution between N2, NH3 and HCN 81 6.4.2 Case 2: calculated equilibrium distribution between NH3 and HCN 83 6.5 Summary 84 7 Traces of BTEX, PAHs and soot in quench water 86 7.1 Quench water behaviour 87 7.2 BTEX compounds 88 7.2.1 BTEX in quench water effluent 90 7.3 PAH compounds 93 7.3.1 PAHs in quench water effluent 95 7.4 Soot formation 99 7.4.1 Soots in quench water effluent 101 7.5 Summary 102 8 Summary and outlook 103 Bibliography 106 9 Appendix 135 List of Figures Figure 2.1: HP POX test plant main facility components and material flow courtesy of [Lurgi GmbH, 2008] 6 Figure 2.2: Simplified scheme of HP POX plant (including quench system) [Lurgi GmbH, 2008] 7 Figure 2.3: Overview of reactions of methane 10 Figure 3.1: Simplified scheme for HP POX quench water system 18 Figure 3.2: Aspen Plus flow diagrams of simulated HP POX quench water system 19 Figure 3.3: Integration of information and functions in VBA via Microsoft Excel to Aspen Plus model 25 Figure 3.4: Integration of information and functions in Python via Microsoft Excel to Aspen Plus model 26 Figure 3.5: ASW enables Excel users to rapidly run scenarios using the underlying rigorous models to analyze plant data, monitor performance, and make better decisions. 27 Figure 4.1: Vapour-liquid equilibria system of CO2, H2S, NH3, HCN and organic acids in the quench water and extended mechanisms according to [Kamps et al., 2001], [Alvaro et al., 2000], [Kuranov et al., 1996], [Xia et al., 1999] and [Edwards et al., 1978]. 30 Figure 4.2: HP POX quench water system with pH regulator for sensitivity studies 34 Figure 4.3: Henry´s constant for CO2, H2S, NH3 and HCN derived from [Edwards et al., 1978] for CO2, [Alvaro et al., 2000] for NH3, [Kamps et al., 2001] for H2S, and [Rumpf et al., 1992] for HCN 35 Figure 4.4: Dissociation constants for CO2, H2S, NH3, HCN and H2O derived from [Alvaro et al., 2000], [Kamps et al., 2001], and [Edwards et al., 1978] 37 Figure 4.5: The flow of CO2 in the quench water cycle (test point VP1). 40 Figure 4.6: Calculated quench water temperature variation and effects on CO2 distribution 42 Figure 4.7: Calculated influence of pH regulation and effects on CO2 distribution 43 Figure 4.8: The flow of NH3 in the quench water cycle (test point VP1). 46 Figure 4.9: Calculated quench water temperature variation and effects on NH3 distribution 47 Figure 4.10: Calculated influence of pH regulation and effects on NH3 distribution 48 Figure 4.11: The flow of HCN in the quench water cycle (test point VP1). 49 Figure 4.12: Calculated quench water temperature variation and effects on HCN distribution 50 Figure 4.13: Calculated influence of pH regulation and effects on HCN distribution 51 Figure 4.14: The flow of H2S in the quench water cycle (test point VP1) 53 Figure 4.15: Calculated quench water temperature variation and effects on H2S distribution 54 Figure 4.16: Calculated influence of pH regulation and effects on H2S distribution 55 Figure 5.1: Aspen Plus back-calculated (real) formic acid concentration, quench water temperature and the calculated equilibrium formic acid concentration against back-calculated (real) ammonia concentration for the 47 test points (using amongst others sampled HCOO- and NH4+ values according to Table 2.6). 59 Figure 5.2: Aspen plus back-calculated (real) formic acid concentration, back-calculated (real) ammonia concentration and the calculated equilibrium formic acid concentration against quench water temperature for the 47 test points (using amongst others sampled HCOO- and NH4+ values according to Table 2.6). 60 Figure 5.3: Aspen plus back-calculated (real) acetic acid concentration, quench water temperature and the calculated equilibrium acetic acid concentration against back-calculated (real) ammonia concentration for the 47 test points. 61 Figure 5.4: Aspen plus back-calculated (real) acetic acid concentration, back-calculated (real) ammonia concentration and the calculated equilibrium acetic acid concentration against quench water temperature for the 47 test points. 62 Figure 5.5: Concentration of formic acid (Aspen plus calculated m_eq and back-calculted m_real) formation in the quench and quench water temperature for the 47 test points. 64 Figure 5.6: Concentration of formic acid (Aspen plus calculated m_eq and back-calculted m_real) in the quench against quench water temperature for the 47 test points (as in Fig.5.2). 65 Figure 5.7: Comparison between formic acid equilibrium constant (Keq), reaction quotient (Kreal) and the quench water temperature for the 47 test points. 66 Figure 5.8: Comparison between formic acid equilibrium constant (Keq) and reaction quotient (Kreal) against quench water temperatures for the 47 test points. 67 Figure 5.9: Concentration of acetic acid (Aspen plus calculated m_eq and back-calculted m_real) in the quench and quench water temperature for the 47 test points. 69 Figure 5.10: Concentration of acetic acid (Aspen plus calculated m_eq and back-calculted m_real) in the quench against quench water temperature for the 47 test points (as in Fig.5.4). 70 Figure 5.11: Comparison between acetic acid equilibrium constant (Keq), reaction quotient (Kreal) and the quench water temperature for the 47 test points. 71 Figure 5.12: Comparison between acetic acid equilibrium constant (Keq) and reaction quotient (Kreal) against quench water temperatures for the 47 test points. 72 Figure 6.1: Mole fraction of gas compoents in the hot gas outlet out of gasifier against hot gas temperature for the 47 test points 76 Figure 6.2: Calculated reaction quotient (Q) and equlibrium constant (Keq) for NH3 against hot gas temperature for the 47 test points (see Fig. 9.10 in Appendix) 77 Figure 6.3: NH3 temperature approach against hot gas temperature for the 47 test points (see Fig. 9.11 in Appendix) 78 Figure 6.4: Calculated reaction quotient (Q) and equlibrium constant (Keq) for HCN against hot gas temperature for the 47 test points (see Fig. 9.13 in Appendix) 79 Figure 6.5: HCN temperature approach against hot gas temperature for the 47 test points (see Fig. 9.14 in Appendix) 80 Figure 6.6: Comparison between calculated real and equilibrium hot gas N2, NH3 and HCN mol fractions against their respective hot gas temperature (case 1). 82 Figure 6.7: Relations between back-calculated real and equilibrium hot gas N2, NH3 and HCN mol fractions (for chemical equilibrium according to equations (6.1) and (6.4)) against their respective hot gas temperature (see Case 1, Section 6.4.1, and Fig. 6.6) 82 Figure 6.8: Comparison between calculated real and equilibrium hot gas HCN mol fraction against their respective hot gas temperature (case 2). 83 Figure 6.9: Relations between back-calculated real and equilibrium hot gas HCN mol fractions, and change in NH3 mol fractions (for chemical equilibrium according to equation (6.4)), against their respective hot gas temperature (see. Case 2, Section 6.4.2 and Fig. 6.7) 84 Figure 6.10 Comparison between NH3 and HCN formation (mole fraction) calculated equilibrium constant (Keq) and calculated reaction quotient (Q), N2 consumption and hot gas temperatures for the 47 test points (case 1 and case 2). 85 Figure 7.1: HP POX test plant quench water system 88 Figure 7.2: Traces of BTEX measured in the Gas-POX 203 – 207 quench water effluent sample. 91 Figure 7.3: Individual component of BTEX measured in the Gas-POX 203 – 207 quench water effluent sample. 92 Figure 7.4: (a) Alkyl radical decomposition and (b) C1 and C2 hydrocarbons oxidation mechanism [Warnatz et al., 2000] 93 Figure 7.5: Recombination of C3H3 to form benzene 94 Figure 7.6: The Diels - Alder reaction for the formation of PAHs 95 Figure 7.7: Amount of PAHs that were detected in Gas-POX 203 – 207 test points quench water effluent samples. 97 Figure 7.8: Distribution of PAH compounds in Gas-POX 203 – 207 quench water effluent samples. 98 Figure 7.9: Some steps in soot formation [McEnally et al., 2006]. 99 Figure 7.10: Illustration of soot formation path in homogenous mixture [Bockhorn et al., 1994] 100 Figure 9.1: Aspen flow sheet set up for HP POX quench system GasPOX 201 VP1 (simplified and extension of Fig. 3.2, organic acids not taken into account). Tabulated values are given in Table 9.11. 135 Figure 9.2: Comparison between the Henry´s constant profiles: Aspen Plus (markers) and Literatures (solid lines) ([Edwards et al., 1978] for CO2, [Alvaro et al., 2000] for NH3, [Kamps et al., 2001] for H2S, and [Rumpf et al., 1992] for HCN as it can be seen in Fig. 4.3) 137 Figure 9.3: Henry´s constant profiles derived from literatures ([Edwards et al., 1978] for CO2, [Alvaro Pérez-Salado et al., 2000] for NH3, [Kamps et al., 2001] for H2S, and [Rumpf et al., 1992] for HCN as it can be seen in Fig. 4.3) 137 Figure 9.4: Comparison between the dissociation constant profiles: Aspen Plus (markers) and Literatures (solid or dashed lines) [Alvaro et al., 2000], [Kamps et al., 2001], and [Edwards et al., 1978] as in Fig.4.4. 138 Figure 9.5: Dissociation constant profiles derived from literatures [Kamps et al., 2001], and [Edwards et al., 1978] as in Fig.4.4. 138 Figure 9.6: Calculated pH values, temperature range and species 139 Figure 9.7: Aspen Plus flow sheet setup for organic acid compounds calculations (GasPOX 201 VP1, see also Table 9.12) 142 Figure 9.8: Aspen Plus flow sheet setup for nitrogen compounds calculations (GasPOX 201 VP1, see also Table 9.12, organic acids are taken into account in the aqueous streams of the quench system) 145 Figure 9.9: Yield of ammonia in gasifier (calculated real) and hot gas temperature against the 47 test points 146 Figure 9.10: Kreal or reaction quotient for ammonia formation in the gasifier against the 47 test points. 146 Figure 9.11: Temperature approach studies for ammonia and the 47 test points 147 Figure 9.12: Yield of HCN from the gasifier (calculated real and equilibrium) and hot gas temperature and the 47 test points 147 Figure 9.13: Comparison between equilibrium constant and reaction quotient for HCN and 47 test points 148 Figure 9.14: Temperature approach studies for HCN and the 47 test points 148 Figure 9.15: Comparison among equilibrium constants of reactions against temperature, T [°C] 149 Figure 9.16: Comparison among equilibrium constants of reactions against temperature, 1/T [1/K] 150 List of Tables Table 2.1: Outline of Gas-POX mode operating parameter range 8 Table 2.2: Outline of test runs operating mode and parameters of chosen test campaigns 9 Table 2.3: Natural gas feedstock compositions 12 Table 2.4: Product synthesis gas analysis method (hot gas before quench) [Brüggemann, 2010] 12 Table 2.5: Analysis methods for raw synthesis gas [Brüggemann, 2010] 13 Table 2.6: Analysis methods for aqueous phase products [Brüggemann, 2010] 14 Table 2.7: Relative accuracy for the measured value for temperature, pressure and flow of each feed and product stream [Meyer, 2007] and [Brüggemann, 2010] 17 Table 3.1: Description of blocks used in Aspen Plus simulation. 20 Table 3.2: HP POX test plant quench water cycle parameters Gas-POX 201 VP1* 23 Table 3.3: pH regulator parameters 24 Table 4.1: Organic acids distribution in streams for VP1 based on calculation from Aspen Plus. 38 Table 4.2: The distribution of CO2 and its ions in all the streams 40 Table 4.3: The distribution of NH3 and its ions in all the streams 45 Table 4.4: The distribution of HCN and its ions in all the streams 49 Table 4.5: The distribution of H2S and its ions in all the streams 52 Table 7.1: Relative sooting tendency [Tesner et al., 2010] 101 Table 9.1: Natural gas feed analysis method [Brüggemann, 2010] 135 Table 9.2: pH scale with examples of solution [NALCO 2008] 136 Table 9.3: Gas-POX test campaigns and with designated serial numbers 140 Table 9.4: Summary of correlation coefficient (r) from Figures in Chapter 5 144 Table 9.5: Comparison among reactions temperatures and heat of reactions 149 Table 9.6: Content of BTEX compounds in Gas-POX quench water samples 151 Table 9.7: BTEX in quench water effluent samples results 152 Table 9.8: Content of PAH compounds in Gas-POX quench water samples 157 Table 9.9: PAHs in quench water effluent samples results 160 Table 9.10: Soot in quench water effluent samples results 169 Table 9.11: Aspen Plus flow sheet setup stream details (GasPOX 201 VP1, according to Fig.3.2 and Fig.9.1, organic acids not taken into account) 170 Table 9.12: Aspen Plus flow sheet setup for organic acid and nitrogen compounds calculations for GasPOX 201 VP1 (according to Figures 9.7 and 9.8, organic acids are taken into account) 174

In den Jahren 2005 bis 2010 erfolgte im Rahmen der Erarbeitung der vorliegenden Dissertationsschrift eine ökologische Untersuchung der Chironomidenfauna in der Talsperre Saidenbach (Sachsen, Erzgebirge). Drei Arten mit hoher Abundanz konnten bei der umfassenden Artenanalyse im Jahr 2005 ermittelt werden: Procladius crassinervis, P. choreus und Chironomus anthracinus. Zusätzlich wurde die Art C. plumosus aufgrund ihrer engen Verwandtschaft zu C. anthracinus in die Untersuchung einbezogen. Die Arbeit ist auf vier Schwerpunkte fokussiert, wobei die Larven und Puppen der vier Arten analysiert wurden. (1) Die Erarbeitung einer zuverlässigen Methode zur Unterscheidung der Larven der beiden eng verwandten Procladius-Arten basierend auf morphologischen Kriterien (Imaginalscheiden-entwicklung, Kopfkapselgröße und Körperlänge) sowie die Tiefenverteilung der Puppen waren eine Vorbedingung für weiterführende Analysen des Lebenszyklus (LZ) dieser beiden Arten. (2) Die Untersuchung des LZ war der zweite Schwerpunkt. Der LZ wurde stark von abiotischen Faktoren wie Temperatur, Sauerstoff und Biovolumen des Phytoplanktons kontrolliert. (3) Die raum-zeitlichen Verteilungsmuster der vier Arten wurden zunächst bezüglich großräumiger Unterschiede über einen Tiefengradienten innerhalb eines Transektes analysiert. Hierbei zeigte sich bei allen vier Arten eine zeitliche Änderung im jeweiligen Hauptverbreitungsgebiet. Die jungen Larven von C. anthracinus, C. plumosus und P. choreus wanderten im Verlauf ihrer Entwicklung bis zur Verpuppung in flachere Bereiche, P. crassinervis wanderte in tiefere Bereiche. Die Analyse der Verteilungsunterschiede der Larven zwischen zwei verschieden stark eutrophierten Buchten ergab höhere Dichten der beiden Chironomus-Arten in der Bucht mit dem größeren Zulauf und der höheren Phytoplanktonkonzentration im Vergleich mit den anderen Arten. Eine Analyse des kleinräumigen Verteilungsmusters fokussierte auf der Frage, ob die Larven gleichmäßig verteilt oder aggregiert auftraten. Die Untersuchung des vertikalen Verteilungsmusters erforschte das Schwimmverhalten der Larven. (4) Der letzte Aspekt war eine experimentelle Untersuchung, die am Beispiel von C. anthracinus durchgeführt wurde mit dem Ziel, den Proximatfaktor für die beobachtete Wanderung der Larven zu ermitteln, der letztendlich die Temperatur war. Puppen bevorzugten im Experiment wärmere Temperaturen und junge Larven kühlere Temperaturen. Die fünfjährige Untersuchung der Chironomiden in der Talsperre Saidenbach beschreibt insgesamt die komplexe Verhaltensreaktion der Chironomiden, die einen wesentlichen Teil der benthischen Lebensgemeinschaft darstellen, bezüglich der Lebenszyklusmuster (Voltinismus, Verpuppung), der Abundanzänderungen (inner- und zwischenjährlich) sowie der groß- und kleinräumigen Verteilung unter der Einwirkung der wichtigsten Umweltfaktoren. / In the context of the present dissertation an ecological study was performed about chironomids in Saidenbach Reservoir in the Saxony Ore Mountains, Germany during the five years from 2005 to 2010. A preliminary overall species analysis in 2005 showed that three species were most abundant: Procladius crassinervis, P. choreus and Chironomus anthracinus. Additionally, the species C. plumosus was examined because of its close relationship to C. anthracinus. The study is focussed on four subjects, whereby larvae and pupae of the four species were analysed. (1) The elaboration of a reliable method to distinguish the larvae of the two closely related species P. crassinervis and P. choreus on the basis of morphological criteria (imaginal disc development, larval head capsule size and body length) as well as the depth distribution of their pupae was a precondition to the profound analysis of their life cycles. (2) The investigation of the life cycle pattern of the four species was the second focus. The life cycle of the four species was found to be strongly influenced by abiotic conditions such as temperature, oxygen and biovolume of the phytoplankton. (3) The spatial and temporal distribution pattern of the four species was analysed in view of large scale differences over a depth gradient in one transect. Here, in all four species a shift in the mainly settled lake bottom area occurred. The young larvae of C. anthracinus, C. plumosus and P. choreus migrated during maturing and pupation towards shallower areas; P. crassinervis migrated to deeper areas. The distribution differences between two different bays showed that the two Chironomus species had higher densities in the bay with the higher inflow which resulted in a higher phytoplankton standing stock compared to the other species. A small scale distribution pattern analysis focussed on finding out whether the larvae were aggregated or randomly distributed. The vertical distribution analysis examined the swimming behaviour of the larvae. (4) The last aspect was an experimental setup exemplarily driven with C. anthracinus which showed that the migration was stimulated by the proximate factor temperature as pupae preferred warmer temperatures and young larvae colder temperatures. Altogether, the five year study about chironomids in Saidenbach Reservoir pointed out the complex reaction in the behaviour of an important part of the benthic community concerning the life cycle pattern (voltinism, pupation pattern), the changing in abundances (inter-annual and intra-annual) and the large scale and small scale distribution pattern under the rule of the most important environmental factors.

In den Jahren 2005 bis 2010 erfolgte im Rahmen der Erarbeitung der vorliegenden Dissertationsschrift eine ökologische Untersuchung der Chironomidenfauna in der Talsperre Saidenbach (Sachsen, Erzgebirge). Drei Arten mit hoher Abundanz konnten bei der umfassenden Artenanalyse im Jahr 2005 ermittelt werden: Procladius crassinervis, P. choreus und Chironomus anthracinus. Zusätzlich wurde die Art C. plumosus aufgrund ihrer engen Verwandtschaft zu C. anthracinus in die Untersuchung einbezogen. Die Arbeit ist auf vier Schwerpunkte fokussiert, wobei die Larven und Puppen der vier Arten analysiert wurden. (1) Die Erarbeitung einer zuverlässigen Methode zur Unterscheidung der Larven der beiden eng verwandten Procladius-Arten basierend auf morphologischen Kriterien (Imaginalscheiden-entwicklung, Kopfkapselgröße und Körperlänge) sowie die Tiefenverteilung der Puppen waren eine Vorbedingung für weiterführende Analysen des Lebenszyklus (LZ) dieser beiden Arten. (2) Die Untersuchung des LZ war der zweite Schwerpunkt. Der LZ wurde stark von abiotischen Faktoren wie Temperatur, Sauerstoff und Biovolumen des Phytoplanktons kontrolliert. (3) Die raum-zeitlichen Verteilungsmuster der vier Arten wurden zunächst bezüglich großräumiger Unterschiede über einen Tiefengradienten innerhalb eines Transektes analysiert. Hierbei zeigte sich bei allen vier Arten eine zeitliche Änderung im jeweiligen Hauptverbreitungsgebiet. Die jungen Larven von C. anthracinus, C. plumosus und P. choreus wanderten im Verlauf ihrer Entwicklung bis zur Verpuppung in flachere Bereiche, P. crassinervis wanderte in tiefere Bereiche. Die Analyse der Verteilungsunterschiede der Larven zwischen zwei verschieden stark eutrophierten Buchten ergab höhere Dichten der beiden Chironomus-Arten in der Bucht mit dem größeren Zulauf und der höheren Phytoplanktonkonzentration im Vergleich mit den anderen Arten. Eine Analyse des kleinräumigen Verteilungsmusters fokussierte auf der Frage, ob die Larven gleichmäßig verteilt oder aggregiert auftraten. Die Untersuchung des vertikalen Verteilungsmusters erforschte das Schwimmverhalten der Larven. (4) Der letzte Aspekt war eine experimentelle Untersuchung, die am Beispiel von C. anthracinus durchgeführt wurde mit dem Ziel, den Proximatfaktor für die beobachtete Wanderung der Larven zu ermitteln, der letztendlich die Temperatur war. Puppen bevorzugten im Experiment wärmere Temperaturen und junge Larven kühlere Temperaturen. Die fünfjährige Untersuchung der Chironomiden in der Talsperre Saidenbach beschreibt insgesamt die komplexe Verhaltensreaktion der Chironomiden, die einen wesentlichen Teil der benthischen Lebensgemeinschaft darstellen, bezüglich der Lebenszyklusmuster (Voltinismus, Verpuppung), der Abundanzänderungen (inner- und zwischenjährlich) sowie der groß- und kleinräumigen Verteilung unter der Einwirkung der wichtigsten Umweltfaktoren.:1. GENERAL INTRODUCTION 2. MORPHOLOGICAL DIFFERENTIATION OF TWO PROCLADIUS AND TWO CHIRONOMUS SPECIES IN THE MESOTROPHIC SAIDENBACH RESERVOIR 2.1 Introduction 2.2 Material and methods 2.2.1 Sampling of larvae 2.2.2 Species identification 2.2.3 Differentiation of the Procladius species by means of head capsule size and depth distribution 2.2.4 Other morphological criteria 2.2.5 Development of imaginal discs 2.3. Results 2.3.1 Procladius crassinervis and P. choreus 2.3.2 Chironomus anthracinus and C. plumosus 2.4. Discussion 2.4.1 Method discussion 2.4.2 Head capsule width 2.4.3 Larval growth 3. FIVE - YEAR LIFE CYCLE PATTERN OF TWO PROCLADIUS AND TWO CHIRONOMUS SPECIES IN THE MESOTROPHIC SAIDENBACH RESERVOIR 3.1 Introduction 3.2 Material and methods 3.2.1 Study area 3.2.2 Sampling of chironomid larvae 3.2.3 Sampling of chironomid pupae 3.2.4 Mortality 3.2.5 Abiotic conditions and phytoplankton 3.3 Results 3.3.1 Abiotic conditions and phytoplankton 3.3.1.1 Temperature 3.3.1.2 Oxygen 3.3.1.3 Phytoplankton 3.3.2 Life cycle analysis 3.3.2.1 Composition of instars 3.3.2.2 Procladius crassinervis 3.3.2.3 Procladius choreus 3.3.2.4 Chironomus anthracinus 3.3.2.5 Chironomus plumosus 3.3.2.6 Tanytarsini 3.3.2.7 Other species 3.3.3 Influence of abiotic conditions on pupation and life cycle 3.3.3.1 Procladius crassinervis 3.3.3.2 Procladius choreus 3.3.3.3 Chironomus anthracinus 3.3.3.4 Chironomus plumosus 3.3.3.5 Tanytarsini 3.3.4 Mortality of larvae during pupation 3.4 Discussion 3.4.1 Method discussion 3.4.2 Life cycle 3.4.3 Influence of controlling factors 3.4.4 Larval mortality and chironomid pupae as prey 4. SMALL AND LARGE SCALE DISTRIBUTION ASPECTS AND MIGRATION OF TWO PROCLADIUS AND TWO CHIRONOMUS SPECIES IN THE MESOTROPHIC SAIDENBACH RESERVOIR 4.1 Introduction 4.2 Study area 4.3 Material and methods 4.3.1 Sampling of chironomid pupae 4.3.2 Sampling of chironomid larvae 4.3.3 Large scale distribution 4.3.3.1 Depth gradient of the larval abundance 4.3.3.2 Distribution between different lake areas 4.3.4 Small scale distribution - patchiness 4.3.5 Vertical distribution 4.3.5.1 Residence depth in the sediment 4.3.5.2 Larvae in the water column 4.4 Results 4.4.1 Large scale distribution 4.4.1.1 Depth gradient of the larval abundance 4.4.1.2 Distribution between different lake areas 4.4.2 Small scale distribution - patchiness 4.4.3 Vertical distribution 4.4.3.1 Residence depth in the sediment 4.4.3.2 Larvae in the water column 4.5 Discussion 4.5.1 Large scale distribution 4.5.1.1 Depth gradient of the larval abundance 4.5.1.2 Distribution between different lake areas 4.5.2 Small scale distribution - patchiness 4.5.3 Vertical distribution 4.5.3.1 Residence depth in the sediment 4.5.3.2 Larvae in the water column 5. INVESTIGATIONS ON THE PREFERENCE TEMPERATURE OF C. ANTHRACINUS FROM THE MESOTROPHIC SAIDENBACH RESERVOIR 5.1 Introduction 5.2 Material and methods 5.2.1 Influence of temperature on the timing of pupation 5.2.2 Preference temperature 5.2.3 Locomotory activity of larvae 5.3 Results 5.3.1 Migratory activity of C. anthracinus in the field 5.3.2 Influence of temperature on the timing of pupation 5.3.3 Preference temperature 5.3.4 Locomotory activity of larvae 5.4 Discussion 5.4.1 Influence of temperature on the timing of pupation 5.4.2 Preference temperature 5.4.3 Agitation activity of larvae 6. OVERALL SUMMARY AND FUTURE PROSPECTS 7. REFERENCES EIDESSTATTLICHE ERKLÄRUNG DANKSAGUNG / In the context of the present dissertation an ecological study was performed about chironomids in Saidenbach Reservoir in the Saxony Ore Mountains, Germany during the five years from 2005 to 2010. A preliminary overall species analysis in 2005 showed that three species were most abundant: Procladius crassinervis, P. choreus and Chironomus anthracinus. Additionally, the species C. plumosus was examined because of its close relationship to C. anthracinus. The study is focussed on four subjects, whereby larvae and pupae of the four species were analysed. (1) The elaboration of a reliable method to distinguish the larvae of the two closely related species P. crassinervis and P. choreus on the basis of morphological criteria (imaginal disc development, larval head capsule size and body length) as well as the depth distribution of their pupae was a precondition to the profound analysis of their life cycles. (2) The investigation of the life cycle pattern of the four species was the second focus. The life cycle of the four species was found to be strongly influenced by abiotic conditions such as temperature, oxygen and biovolume of the phytoplankton. (3) The spatial and temporal distribution pattern of the four species was analysed in view of large scale differences over a depth gradient in one transect. Here, in all four species a shift in the mainly settled lake bottom area occurred. The young larvae of C. anthracinus, C. plumosus and P. choreus migrated during maturing and pupation towards shallower areas; P. crassinervis migrated to deeper areas. The distribution differences between two different bays showed that the two Chironomus species had higher densities in the bay with the higher inflow which resulted in a higher phytoplankton standing stock compared to the other species. A small scale distribution pattern analysis focussed on finding out whether the larvae were aggregated or randomly distributed. The vertical distribution analysis examined the swimming behaviour of the larvae. (4) The last aspect was an experimental setup exemplarily driven with C. anthracinus which showed that the migration was stimulated by the proximate factor temperature as pupae preferred warmer temperatures and young larvae colder temperatures. Altogether, the five year study about chironomids in Saidenbach Reservoir pointed out the complex reaction in the behaviour of an important part of the benthic community concerning the life cycle pattern (voltinism, pupation pattern), the changing in abundances (inter-annual and intra-annual) and the large scale and small scale distribution pattern under the rule of the most important environmental factors.:1. GENERAL INTRODUCTION 2. MORPHOLOGICAL DIFFERENTIATION OF TWO PROCLADIUS AND TWO CHIRONOMUS SPECIES IN THE MESOTROPHIC SAIDENBACH RESERVOIR 2.1 Introduction 2.2 Material and methods 2.2.1 Sampling of larvae 2.2.2 Species identification 2.2.3 Differentiation of the Procladius species by means of head capsule size and depth distribution 2.2.4 Other morphological criteria 2.2.5 Development of imaginal discs 2.3. Results 2.3.1 Procladius crassinervis and P. choreus 2.3.2 Chironomus anthracinus and C. plumosus 2.4. Discussion 2.4.1 Method discussion 2.4.2 Head capsule width 2.4.3 Larval growth 3. FIVE - YEAR LIFE CYCLE PATTERN OF TWO PROCLADIUS AND TWO CHIRONOMUS SPECIES IN THE MESOTROPHIC SAIDENBACH RESERVOIR 3.1 Introduction 3.2 Material and methods 3.2.1 Study area 3.2.2 Sampling of chironomid larvae 3.2.3 Sampling of chironomid pupae 3.2.4 Mortality 3.2.5 Abiotic conditions and phytoplankton 3.3 Results 3.3.1 Abiotic conditions and phytoplankton 3.3.1.1 Temperature 3.3.1.2 Oxygen 3.3.1.3 Phytoplankton 3.3.2 Life cycle analysis 3.3.2.1 Composition of instars 3.3.2.2 Procladius crassinervis 3.3.2.3 Procladius choreus 3.3.2.4 Chironomus anthracinus 3.3.2.5 Chironomus plumosus 3.3.2.6 Tanytarsini 3.3.2.7 Other species 3.3.3 Influence of abiotic conditions on pupation and life cycle 3.3.3.1 Procladius crassinervis 3.3.3.2 Procladius choreus 3.3.3.3 Chironomus anthracinus 3.3.3.4 Chironomus plumosus 3.3.3.5 Tanytarsini 3.3.4 Mortality of larvae during pupation 3.4 Discussion 3.4.1 Method discussion 3.4.2 Life cycle 3.4.3 Influence of controlling factors 3.4.4 Larval mortality and chironomid pupae as prey 4. SMALL AND LARGE SCALE DISTRIBUTION ASPECTS AND MIGRATION OF TWO PROCLADIUS AND TWO CHIRONOMUS SPECIES IN THE MESOTROPHIC SAIDENBACH RESERVOIR 4.1 Introduction 4.2 Study area 4.3 Material and methods 4.3.1 Sampling of chironomid pupae 4.3.2 Sampling of chironomid larvae 4.3.3 Large scale distribution 4.3.3.1 Depth gradient of the larval abundance 4.3.3.2 Distribution between different lake areas 4.3.4 Small scale distribution - patchiness 4.3.5 Vertical distribution 4.3.5.1 Residence depth in the sediment 4.3.5.2 Larvae in the water column 4.4 Results 4.4.1 Large scale distribution 4.4.1.1 Depth gradient of the larval abundance 4.4.1.2 Distribution between different lake areas 4.4.2 Small scale distribution - patchiness 4.4.3 Vertical distribution 4.4.3.1 Residence depth in the sediment 4.4.3.2 Larvae in the water column 4.5 Discussion 4.5.1 Large scale distribution 4.5.1.1 Depth gradient of the larval abundance 4.5.1.2 Distribution between different lake areas 4.5.2 Small scale distribution - patchiness 4.5.3 Vertical distribution 4.5.3.1 Residence depth in the sediment 4.5.3.2 Larvae in the water column 5. INVESTIGATIONS ON THE PREFERENCE TEMPERATURE OF C. ANTHRACINUS FROM THE MESOTROPHIC SAIDENBACH RESERVOIR 5.1 Introduction 5.2 Material and methods 5.2.1 Influence of temperature on the timing of pupation 5.2.2 Preference temperature 5.2.3 Locomotory activity of larvae 5.3 Results 5.3.1 Migratory activity of C. anthracinus in the field 5.3.2 Influence of temperature on the timing of pupation 5.3.3 Preference temperature 5.3.4 Locomotory activity of larvae 5.4 Discussion 5.4.1 Influence of temperature on the timing of pupation 5.4.2 Preference temperature 5.4.3 Agitation activity of larvae 6. OVERALL SUMMARY AND FUTURE PROSPECTS 7. REFERENCES EIDESSTATTLICHE ERKLÄRUNG DANKSAGUNG