The introduction of ceramics into the market of wood cutting tools has failed so far due to the generally low toughness of ceramics which is causing brittle failure of the cutting edge. A feasibility study showed that Si3N4/SiC composites with fine elongated β-Si3N4 grains are a promising material for industrial wood machining and outperform commercial standard tungsten carbide tools in terms of lifetime. However, they were produced by hot pressing followed by very costly diamond cutting and grinding. The costs associated with the above production route are too high for an industrial viability. In this thesis Si3N4/SiC composites suitable for industrial wood milling are produced by a near net shape processing route including gas pressure sintering. These newly developed tools show less abrasive wear and consequently twice as long lifecycles than commercial standard tungsten carbide tools. Microscopic properties determine the performance of the Si3N4/SiC cutting tools. Therefore, an adequate selection of sintering additives is crucial. 12 wt% sintering additives are included in the composite as a combination of Al2O3 and the refractory oxides La2O3 and Y2O3. Important for the production of effective Si3N4/SiC wood cutting tools is the formation of a partly crystalline silicate phase within the multiple grain junctions during the final treatment by hot isostatic pressing. The use of MgO as a sintering additive for facilitating the densification of the Si3N4 ceramics inhibits the formation of the favourable silicate phase and must be avoided for the production of these wood cutting tools.

Natural composites, in particular nacre, often combine high strength and toughness thanks to highly ordered architectures and controlled geometries of the reinforcement components. However, combining strength, toughness and resorbability in synthetic materials remains a challenge in particular in the field of bone graft substitutes. In the present study, calcium phosphate-(CaP-)based materials with designed architectures inspired from natural composite materials were achieved. CaP platelets obtained by precipitation in organic medium were first aligned in chitosan matrices by solvent casting in ambient conditions. Efficient strengthening was obtained with 15 vol-% ceramic, reaching cortical bone strength (150 MPa) and preserving good ductility (5 % deformation). In a weak magnetic field, high spatial arrangement without percolation was maintained up to 20 vol-%. With directional freezing, good alignment of the platelets could be pushed up to 50 vol-%. In parallel, in situ recrystallization of CaP blocks in hydrothermal conditions led to hierarchical structures. The strength and the work-of-fracture were enhanced (300%) thanks to a change of failure mode.:Acknowledgements v Summary vii Background vii Thesis outline viii Part I: “Brick-and-mortar” structures with discrete reinforcement components ix Part II: “Textured” structures with continuous reinforcement components x Zusammenfassung xi Hintergrund xi Doktorarbeit Gliederung xii Teil I: “Ziegelmauer-Architektur” mit diskreten Verstärkungskomponenten xiii Teil II: “ Texturierte” Strukturen mit kontinuierlichen Verstärkungskomponenten xiv Chapter 1: General introduction 1 Bone grafting 1 CaP ceramics 1 How to improve toughness of CaP ceramics? 2 Importance of structure design: bio-inspiration 2 What mechanical properties should be reached? 5 Specific aims 5 Two general approaches to reach the goal 6 Nacre-inspired “brick-and mortar” structures (Part I) 6 Textured ceramic monoliths (Part II) 6 References 7 Chapter 2: Theoretical calculations 11 Introduction 12 Theoretical tensile strength of β-TCP platelets and critical size for flaw tolerance 13 Optimal aspect ratio 15 Composite strength and stiffness 17 Limitations 19 References 19 PART I: NACRE-INSPIRED “BRICK-AND-MORTAR” STRUCTURES Chapter 3: Synthesis of sub-micrometer calcium phosphate platelets 23 Introduction 24 ii Materials and Methods 25 Precipitation method 25 Reaction parameters 25 Characterization 26 Statistical analysis of results 28 Results 28 Reproducibility of standard experiments 28 Increase of the reagent volume to increase the productivity 30 Increase of the precursors concentration to increase the productivity and modify the particles 30 Increase of titration rate to simplify the process 32 Influence of temperature on the particles 35 Effect of the pH value on the particles 37 Effect of a longer reaction time on the particle stability 40 Study of the influence of variations of the Ca/P molar ratio 42 Discussion 43 Reproducibility 43 Productivity 44 CaP crystal shape 45 Crystal purity 47 Aspect ratio 48 Critical thickness 49 Uniformity of primary particles 50 Non agglomerated 51 General points 52 Conclusions 52 References 53 Chapter 4: Kinetics study of the calcium phosphate platelets growth 57 Introduction 58 Theory 58 Materials and methods 60 Materials and sample preparation 60 Characterization methods 61 Results 62 Visual observations during manipulations 62 SEM observations 62 XRD results 66 Size measurements 68 Kinetics calculations 70 Discussion 74 Nucleation and assembly mechanism 74 Reaction kinetics 76 Control of size and aspect ratio 76 Conclusions 77 References 78 Chapter 5: Structural design of bio-inspired composites by solvent casting 81 Foreword 82 Introduction 82 Experimental section 84 iii Synthesis of resorbable ceramic platelets 84 Solvent casting to prove the reinforcement efficiency of DCP platelets 84 Magnetization of the platelets 85 Maintaining the orientation during drying of an hydrogel matrix 86 Results 87 Synthesis of resorbable ceramic platelets 87 Solvent casting to prove the reinforcement efficiency of CaP platelets 87 Magnetization of the platelets 91 Maintaining the orientation during drying of an hydrogel matrix 93 Discussion 95 Detrimental effect of β-TCP platelets in chitosan 95 Efficient reinforcement with DCP platelets up to a given volume fraction 96 Threshold value for strength improvement 97 Fitting the experimental results with theoretical equations 98 Conclusions 101 References 101 Chapter 6: Biodegradable, strong and tough nacre-inspired structures obtained by freezecasting 105 Introduction 106 Experimental section 108 Synthesis of resorbable ceramic platelets 108 Preliminary freeze-casting tests with β-TCP-based slurries 108 Determination of adequate freeze-casting parameters for hydrogels-CaP slurries 108 Integration of CaP platelets and local planar alignment 109 Attempts to globally align porosity in two directions 109 Densification and consolidation 110 Tensile testing 110 Results 111 Preliminary freeze-casting tests with β-TCP-based slurries 111 Determination of adequate freeze-casting parameters for hydrogels-CaP slurries 112 Integration of CaP platelets and local planar alignment 113 Attempts to globally align porosity in two directions 119 Densification and consolidation 121 Tensile testing 121 Discussion 122 Conclusions 124 References 125 PART II: TEXTURED CERAMIC MONOLITHS Chapter 7: Micro-texturing by recrystallization of calcium phosphate blocks in hydrothermal conditions 127 Introduction 128 Materials and Methods 130 Samples characterization 132 Results 133 Macroscopic observations 133 Microstructural changes (SEM) 133 Crystalline phase conversion (XRD) 139 iv Mechanical properties 142 Fractured surfaces 142 Discussion 145 Conclusions 150 References 150 Chapter 8: Toughening of textured calcium phosphate blocks by polymer impregnation 155 Foreword 156 Introduction 156 Materials and Methods 157 Samples preparation 157 Characterization 158 Results 158 Porosity and microstructure 158 Composition 161 Mechanical properties 161 Discussion 162 Conclusions 164 References 164 Chapter 9: Synthesis and outlook 167 Curriculum Vitae 171

We present a mean field model for a mixture of AB diblock-copolymers and A-block selective nanoparticles confined between two identical non-selective walls. A horizontally symmetric lamellar structure of the nanocomposite is considered where nanoparticles are allowed to segregate between the polymer–wall interfaces. For a fixed value of wall separation, we study changes in the free energy as a function of the number of lamellar layers and the amount of nanoparticle uptake in the A-phase denoted by y = ϕx with 0 ≤ x ≤ 1 for a given value of ϕ, where ϕ is the overall nanoparticle volume fraction. The absorption isotherm for nanoparticle uptake in the A-phase as a function of ϕ shows saturation beyond a threshold value ϕs, and the optimal value of uptake y increases with increasing strength of monomer–nanoparticle attractive interaction. Increasing ϕ above ϕs produces a decrease in the optimal number of lamellar layers which is related to a jump-like transition of the chain extension. The effect of varying film thickness is also studied. By considering A-block selective walls we also investigated a wetting transition of the copolymer film and found the transition to be discontinuous. A corresponding phase diagram is constructed. / Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

Emerging contaminants represent newly identified organic chemical pollutants that are not yet covered by routine monitoring and regulatory programs. Current research on these contaminants is greatly hindered by the shortage of analytical methods due to the complex matrices, extremely low concentration and their “emerging” nature. In this study the innovative analytical and monitoring methods have been developed and validated for determination of emerging pollutants in water (including pharmaceutical and personal care products, pesticides and artificial sweeteners) based on graphene-silica composite as the solid-phase extraction (SPE) sorbent and as the receiving phase in passive sampler. Graphene, a new allotropic member in the carbon family, has been considered to be a promising candidate for sorption material with high loading capacity because of its ultra-high specific surface area and large delocalized π-electron-rich structure. The composite employed in this work was synthesized by using the cross-link agent to covalently combine carboxylic acid groups of graphene-oxide with the amino groups of the modified silica gel. Afterwards, graphene-silica composite was obtained after treated with hydrothermal reaction in the microwave autoclave, which was demonstrated by X-ray diffraction (XRD). The analytical procedure entails SPE followed by high performance liquid chromatography equipped with tandem mass spectrometers (HPLC-MS/MS). Several crucial parameters were optimized to improve recovery of the analytes, including the amount of sorbents, the ratio of graphene oxide/amino-silica and pH value of water samples. The best recovery results were achieved with 100 mg 10 % (w/w) graphene-silica composite, which were over 70 % except four artificial sweeteners, ranitidine and triclosan. Compared with its commercial counterpart Oasis HLB, pH value variation of water samples has less effect on the recoveries, making graphene composite to be a potential receiving phase of monitoring tool. The batch-to-batch reproducibility was verified on six independently SPE cartridges with graphene-silica composites from two repeatable synthetic batches, showing relative standard deviations (RSDs) in the range of 8.3 % to 19.1 %, except ibuprofen and saccharin. The cartridges proved to be reusable for at least 10 times consecutive extractions, with RSD < 14.9 %, except ibuprofen and diclofenac. The Chemcatcher® passive sampler is frequently used for monitoring polar organic chemicals in surface water. Uptake kinetics is necessary to be quantified to calculate time-weighted average (TWA) concentration. A series of calibration experiments were conducted in the beaker renewal experiments as well as in the flow-through system with styrenedivinylbenzene-cross connect (SDB-XC) disks and graphene-silica composite as the receiving phase. The results obtained from the beaker renewal experiments showed that the uptake kinetics of accumulated compounds with all Chemcatcher® configurations can keep linear within 2 weeks. The innovative configuration using graphene-silica composite powder placed between two PES membranes was able to accumulate eleven of the selected compounds with uptake rate (Rs) from 0.01 L/day (acesulfame K and sucralose) to 0.08 L/day (chlothianidin), while its commercial counterpart SDB-XC disks with polyethersulfone (PES) membranes can accumulate seven substances with Rs from 0.02 L/day (sucralose and chlothianidin) to 0.15 L/day (carbamazepine). In the flow-through system, when Chemcatchers® were equipped with SDB-XC disks without PES membranes, the linear uptake range for the majority of compounds was only in one week, except atrazine. The Rs of accumulated compounds were from 0.16 L/day (chloramphenicol) to 1.04 L/day (metoprolol) that are higher than the same substances in the beaker renewal experiments, in which the Rs of chloramphenicol and metoprolol were 0.09 L/day and 0.56 L/day respectively. However, if the PES membranes were employed, the uptake kinetics in both calibration experimental designs were comparable: the Rs of accumulated compounds from the configuration with SDB-XC disks covered by PES membranes were from 0.035 L/day (sucralose) to 0.17 L/day (carbamazepine) and from the configuration with graphene-silica composite were from 0.01 L/day (gemfibrozil) to 0.08 L/day (chlothianidin). Moreover, the uptake range can keep linear within two weeks. The developed Chemcatcher® method was successfully applied in real surface waters. 1-H benzontriazole, tolyltriazole and caffeine were the main contaminants in Elbe River and the Saidenbach drinking water reservoir. The investigated results between summer and autumn monitoring period were not significantly different.:Acknowledgement I Abstract III Zusammenfassung V Content IX List of Figures XIII List of Tables XVII Table of Abbreviations XIX 1. Motivation 1 2. Introduction 3 2.1 Emerging contaminants 3 2.1.1 Definition 3 2.1.2 Sources 3 2.1.3 Concern about the adverse impacts 5 2.2 Analysis of the emerging contaminants 7 2.2.1 General analytical process 7 2.2.2 Enrichment techniques 8 2.2.2.1 Liquid-liquid extraction (LLE) 8 2.2.2.2 Solid-phase extraction (SPE) 9 2.2.2.3 Innovative type of solid-phase extraction 13 2.2.3 Analytical methods 15 2.3 Graphene and its application in analytical chemistry 19 2.3.1 Introduction 19 2.3.2 Synthesis methods of graphene 20 2.3.3 Application in sample pre-treatment 21 2.3.3.1 Graphene-based material as SPE sorbent 21 2.3.3.2 Graphene-coated fibers as SPME sorbent 22 2.3.3.3 Magnetic graphene as MSPE sorbent 23 2.3.3.4 Graphene-based MIPs 24 2.4 Chemcatcher®—a passive sampling technique 25 2.4.1 Introduction 25 2.4.2 Theory 26 2.4.2.1 Equilibrium passive sampling 27 2.4.2.2 Kinetic passive sampling 28 2.4.3 Concept of Chemcatcher® 28 2.4.4 Calibration of Chemcatcher® 33 2.4.5 Performance and reference compounds 36 3. Study objectives and hypotheses 39 3.1 Study objectives 39 3.2 Hypotheses 41 4. Material and methods 43 4.1 Materials 43 4.1.1 Chemicals and solutions 43 4.1.2 Consumable materials and instruments 44 4.2 Synthesis of graphene-silica composite 46 4.3 SPE experiments 49 4.3.1 Packing method 49 4.3.2 SPE procedure 49 4.3.3 Optimization of SPE procedures 51 4.3.4 Repeatability and reusability test 52 4.4 Chemcatcher® experiments 53 4.4.1 Preparation and precondition 53 4.4.2 Calibration of Chemcatcher® 55 4.4.2.1 Preliminary test 55 4.4.2.2 Experimental design of the beaker batch tests 56 4.4.2.3 Experimental design of the flow-through system 57 4.4.3 Monitoring application of Chemcatcher® in surface water 59 4.4.4 Elution process 60 4.4.5 Statistic data evaluation 61 4.5 HPLC-MS/MS analysis 62 5. Results and discussion 63 5.1 Preparation and characterization of graphene-silica composite 63 5.2 SPE performance of the graphene-silica composite 67 5.2.1 Preliminary test of packing methods 67 5.2.2 Optimization of SPE procedures 68 5.2.2.1 The amount of sorbent 68 5.2.2.2 Graphene ratio in the composites 68 5.2.2.3 pH value of the water sample 69 5.2.3 Repeatability and reusability test 72 5.2.3.1 Performance of the off-line SPE 72 5.2.3.2 Repeatability and reusability test results 75 5.2.4 Summarized discussion of the SPE performance 76 5.3 Calibrating results of Chemcatcher® 86 5.3.1 Pre-test results 86 5.3.1.1 Feasibility test of commercial disks as receiving phase 86 5.3.1.2 Stability test 88 5.3.1.3 Elution optimization. 88 5.3.1.4 Recovery of the filters 92 5.3.2 Calibration results of renewal experiments 93 5.3.2.1 SDB-XC disks without and with membranes 93 5.3.2.2 Graphene-silica composite as receiving phase 97 5.3.3 Calibration results of the flow-through system experiments 101 5.3.3.1 Determination of experimental parameters 101 5.3.3.2 Concentration control 103 5.3.3.3 Calibration results 105 5.3.3.4 Preliminary evaluation of performance and reference compounds 112 5.4 Application of Chemcatcher® in surface water 114 5.5 Discussion about problems of commercial disks as receiving phase in Chemcatcher® 118 5.5.1 Deformation of commercial disks 118 5.5.2 The particles in the solution after elution 119 6. Conclusion and perspective 121 7. Annex 125 7.1 Material and methods 125 7.1.1 Chemicals 125 7.1.2 Silica gel and graphene oxide 144 7.1.3 Microwave reduction program 144 7.1.4 Working schedule of the calibration experiments in flow-through system 144 7.1.5 HPLC-MS/MS conditions 146 7.2 Experimental results 149 7.2.1 Stability of the colloid solution of graphene oxide 149 7.2.2 EDX analysis results 149 7.2.3 HPLC-MS/MS results 152 7.2.4 Calibrating results of the beaker renewal experiment 153 7.2.5 Calibrating results of the flow-through system experiments 157 7.2.6 Monitoring results in the Elbe River 161 Reference 163

Reliable line production processes and simulation tools play a central role for the structural integration of thermoplastic composites in advanced lightweight constructions. Provided that material- adapted joining technologies are available, they can be applied in heavy-duty multi-material designs (MMD). A load-adapted approach was implemented into the new fully automatic and faulttolerant thermo mechanical flow drill joining (FDJ) concept. With this method it is possible to manufacture reproducible high strength FRP/metal-joints within short cycle times and without use of extra joining elements for the first time. The analysis of FDJ joints requires a simplified model of the joint to enable efficient numerical simulations. The present work introduces a strategy in modeling a finite-element based analogous-approach for FDJ-joints with glass fiber reinforced polypropylene and high-strength steel. Combined with a newly developed section-force related failure criterion, it is possible to predict the fundamental failure behavior in multi-axial stress states. The functionality of the holistic approach is illustrated by a demonstrator that represents a part of a car body-in-white structure. The comparison of simulated and experimentally determined failure loads proves the applicability for several combined load cases.

Poly(3-hydroxybuttersäure-co-3-hydroxyvaleriansäure), PHBV, ist ein Copolyester, der auf biologischem Weg durch Bakterien herstellbar und ein steifes sowie relativ festes Polymer ist. Seine Biokompatibilität und biologische Abbaubarkeit weckt das Interesse für diverse Anwendungen in Pharmazie und Medizin. PHBV reagiert mit Abbau empfindlich auf zugleich thermische und mechanische Belastungen, was ein Problem für die Verarbeitung darstellt. Produkte aus PHBV aus einmal geschmolzenem und verarbeitetem Pulver sind hochkristallin. Daher ist das Material spröde. Ferner wirkt sich die hohe Kristallinität sowie eine große Änderung der Dichte beim Abkühlen der Schmelze nachteilig auf die Spinnbarkeit des Materials aus. Nach dem Passieren der Spinndüse ziehen sich die Spinnfäden zusammen, was die Gefahr eines Fadenrisses beim Spinnen erhöht. Aufgrund der relativ hohen Kristallinität des Materials und einer verzögerten Kristallisationskinetik bei gesponnenen Polymerfäden kommt es zur Nachkristallisation in einem erheblichen Ausmaß, die Fäden verkleben nach dem Aufwickeln auf den Galetten und reißen beim Abwickeln. Zur Behebung der Nachteile wurden Verarbeitungsbedingungen vor allem bei Schmelzspinnprozessen mit der Kolbenspinnanlage und bei Mischungsprozessen optimiert. Die Polymermischungen und ?verbundstoffe enthalten kugelförmige Mikropartikel verschiedener Morphologie, die zuvor synthetisiert und charakterisiert wurden. Vor allem mit Vinylgruppen modifizierte Silikat-Submikropartikel mindern die Sprödigkeit von PHBV.

Powder metallurgy is one way of producing complex, graded structures that could allowmaterial systems to be produced with properties tailored to individual applications. However,powder metallurgy requires that the semi-finished products are very similar to the final component.It is much more economical to produce simple semi-finished products and then combine them bypowder forging and simultaneous compaction than forming complex components with the desiredgraded structure. However, it is absolutely necessary that the graded structure of the semi-finishedproducts is maintained during the forming process. In this study, pre-sintered cylindrical semi-finished products, consisting of axially graded as well as radially graded components, were producedby powder forging at 1100◦C. The microstructures, densities and mechanical properties of the finalcomponents were investigated to verify the effectiveness of the process route. It was observed thatthe components formed solid structures after compaction, in which the reinforcing ZrO2particleswere fully integrated into the transformation-induced plasticity steel matrix.

The PhD thesis provides detailed description of a successful development of MgO and TiO2 particle reinforced Steel Ceramic Composites (SCC) for molten aluminum alloy applications. For this purpose, the influence of MgO and TiO2 addition and subsequent pre-oxidation surface treatment on the structure of SCCs and their corrosion resistance against long-term contact with liquid aluminum alloys was investigated. The initiation and progression of corrosion processes were thoroughly analyzed by means of newly developed DSC-aided corrosion tests, high temperature electrochemical studies and adapted wettability measurements. The gained insights led to the recognition of most important factors contributing to the corrosion, including both the electrochemical and the chemical driving forces arising between the SCCs and aluminum alloy. The evaluation of long-term corrosion resistance was performed with the help of finger immersion tests, crucible corrosion tests and subsequent SEM/EDS/EBSD and XRD analyses aiming at the determination of elements most prone to the dissolution in the liquid aluminum alloy and formation of corrosion phases. The pre-oxidized MgO reinforced SCC revealed superior corrosion resistance, being capable of withstanding more than 168 h of contact with liquid aluminum alloy.:Table of content 1 Introduction 1 2 Theoretical background 5 2.1 Wettability measurements 5 2.2 Electrochemical behavior of SCC/molten aluminum alloy material pair 8 2.3 Steel-based materials/molten aluminum alloy reaction 13 2.4 Long-term corrosion mechanisms 16 2.5 Differential Scanning Calorimetry for corrosion precipitation analysis 18 2.6 Corrosion of steel and SCCs during long-term contact with aluminum alloys 19 2.7 Protective coatings and surface treatment of steel and Steel Ceramic Composites 21 2.7.1 Protective coatings against molten aluminum alloys 21 2.7.2 Oxidation kinetics 22 3 Materials and Methods 25 3.1 Materials and Composites Manufacturing 26 3.2 Investigation of corrosion phase formation via DSC-aided corrosion tests 29 3.3 High temperature electrochemical studies 30 3.4 Elaboration of suitable surface pre oxidation for SCCs 33 3.5 Wettability Tests 34 3.6 Finger immersion tests 35 3.7 Crucible Corrosion Tests 36 4 Results and Discussion 41 4.1 Investigation of corrosion phase formation using DSC-aided corrosion tests 41 4.1.1 Determination of reference information for DSC-aided corrosion test 41 4.1.2 Influence of the sample/melt contact duration on the alteration of DSC signal – elaboration of suitable corrosion test conditions. 44 4.1.3 Investigation of 120 min contact time between 316L40TiO2 and 316L40MgO Steel Ceramic Composites with aluminum alloy on the formation of corrosion phases in the melt 47 4.1.4 SEM/EDS microscopical analysis of 316L sample after DSC-aided corrosion test with AlSi7Mg0.3 aluminum alloy for 120 min 51 4.1.5 SEM/EDS microscopical analysis of 316L40TiO2 sample after DSC-aided corrosion test with AlSi7Mg0.3 aluminum alloy for 120 min 53 4.1.6 SEM/EDS microscopical analysis of 316L40MgO sample after DSC-aided corrosion test with AlSi7Mg0.3 aluminum alloy for 120 min 55 4.2 High temperature electrochemical studies of SCCs 60 4.2.1 Evaluation of thermal and chemical stability of selected three-electrode cell materials 60 4.2.2 Differential Potential 61 4.2.3 Impedance Spectroscopy and Potentiodynamic Polarization 64 4.2.4 Microscopical analysis of WE after the electrochemical experiment 68 4.3 Surface treatment of SCCs 79 4.3.1 Dilatometry and Thermogravimetry of SCCs during pre-oxidation 79 4.3.2 Preliminary evaluation of morphology of the SCCs cross-section after pre oxidation at different temperatures and for different durations 83 4.3.3 Detailed SEM/EDS/XRD structure analysis of selected pre-oxidized SCCs 87 4.4 Wettability of aluminum alloy on SCCs 102 4.4.1 Characterization of substrates surface 102 4.4.2 Wetting angle at the drop release 102 4.4.3 Wetting angle 30 min after reaching 850 °C 104 4.4.4 Evaluation of the droplet/substrate cross-section 105 4.5 Finger Immersion Tests 107 4.5.1 Preliminary evaluation of peroxidized SCCs after immersion test 107 4.5.2 Analysis of 316L40TiO2 immersion sample pre oxidized at 850 °C for 24 h 111 4.5.3 Analysis of 316L40TiO2 immersion sample pre-oxidized at 1000 °C for 24 h 112 4.5.4 Analysis of 316L40MgO immersion sample pre oxidized at 850 °C for 24 h 113 4.5.5 Analysis of 316L40MgO immersion sample pre-oxidized at 1000 C for 24 h 114 4.6 Crucible Corrosion Tests 115 4.6.1 Preliminary evaluation of crucible corrosion test results 115 4.6.2 Analysis of 316L40TiO2 sample pre oxidized at 850 °C for 24 h after the crucible corrosion test for 24 h 119 4.6.3 Analysis of 316L40TiO2 sample pre-oxidized at 1000 °C for 24 h after the crucible corrosion test for 168 h 120 4.6.4 Analysis of 316L40MgO sample pre-oxidized at 850 °C for 24 h after the crucible corrosion test for 24 h 122 4.6.5 Analysis of 316L40MgO sample pre-oxidized at 1000 °C for 24 h after the crucible corrosion test for 168 h 125 4.6.6 Analysis of the microstructure of aluminum alloy after crucible corrosion tests 128 4.6.7 Evaluation of contamination of aluminum alloy after crucible corrosion tests 133 Conclusions 137 References 145 Appendixes 161 Appendix A: Preliminary Investigations 161 A.1: Preparation of SCC granulates 161 A.2: Evaluation of properties of composites pressed from granulates 162 Appendix B: Constructions and Designs 169 B.1. Three-Electrode Cell – for high temperature electrochemical measurements with molten aluminum alloys as reference electrode 169 B.2. Capillary System – for capillary purification technique wettability measurements with aluminum alloys 177 Appendix C: Auxiliary Investigations 184 C.1 Detailed SEM/EDS analysis of pre-oxidized SCCs 184 C.2 SEM/EDS analysis of SCCs after 96 h Finger Immersion Tests in aluminum alloy 207

Kohlenstofffaserverstärkter Kohlenstoff weist ausgezeichnete thermische, mechanische und chemische Eigenschaften auf. Aufgrund seiner Faserarchitektur und Porosität zeigt dieser eine mit metallischen und polymeren Werkstoffen vergleichbar hohe Schadenstoleranz. Die Herstellung komplexer Leichtbaustrukturen aus C/C-Verbunden ist jedoch zeit- und kostenintensiv. Ein neuer Ansatz stellt die Integration geometrisch simpler C/C-Verbunde in komplexe, problemlos zu realisierende polymere Strukturen dar. Ein derartiges Werkstoffkonzept vereint die Vorteile seiner Komponenten in einem ganzheitlichen Werkstoffsystem. Einen Nachteil stellt jedoch die geringe wechselseitige Adhäsion seiner Komponenten dar. Die Innovation dieses Beitrags stellt sich einerseits der Herausforderung die mechanischen Eigenschaften der C/C-Verbunde in Abhängigkeit der intrinsischen Porosität zu beeinflussen. Dies geschieht durch Veränderung der chemischen und physikalischen Vernetzungsbedingungen des Matrixprecursors. Andererseits soll die dadurch herrührende inhärente Porosität zur Vergrößerung der wirksamen äußeren Oberfläche und zur gezielten Verbesserung der Adhäsion zum Polymer führen. Es wird ein Kohlenstoffprecursor mit variabler offener Porosität entwickelt und daraus neuartige verschiedenporöse C/C-Verbunde hergestellt und untersucht. Im Anschluss werden die verschiedenporösen C/C-Verbunde mit ausgewählten Polymeren unter definierten Konsolidierungsparametern thermisch gefügt und deren wechselseitiges Adhäsionsverhalten bewertet. / Fibre-reinforced ceramic matrix composite materials are characterized by excellent thermal, mechanical and chemical properties. Their high tolerance regarding damaging is a result of the intrinsic fibre structure and porosity. Due to this fact, they offer outstanding dampening characteristics, as is the case for polymeric materials. The production of complex structures is very time consuming and expensive. The integration of simple geometric ceramic composite materials in complex polymeric structures is regarded as a new approach for the production of these materials. These easy-to-produce hybrid ceramic/polymer compound materials combine the advantages of ceramics and polymers in one material system. However, one main disadvantage of these materials is the mutual adhesion of the two components. This article deals with the challenge of the manipulation of the mechanical properties of the C/C composites depending on the intrinsic porosity. This is realized by altering the physical and chemical wetting/coating conditions of the matrix precursor. In addition, the inherent porosity is supposed to increase the effective outer surface and specifically improve the adhesion. For this purpose, a novel carbon precursor with an adjustable open porosity is developed and investigated further. During this different versions of the CFRP and various C/C materials of different production steps are produced and examined. The variation of the precursors is supposed to take place in the polymeric state. The different C/C composites are subsequently thermally bonded with selected polymers and defined consolidation parameters. The mutual joining and connection behaviour is investigated further.

Das Elektronenstrahlschweißen im Vakuum hat sich als zuverlässiges Verfahren für die Herstellung schmaler und hochpräziser Schweißnähte beim Schweißen von TRIP-Stählen bewährt. Das Verständnis für die dabei auftretenden Mechanismen und wirkenden Kräfte stellt einen wichtigen Baustein für die Weiterentwicklung des Verfahrens dar. Um zur Erweiterung dieses Verständnisses beizutragen, wird auf Basis vorhandener Berechnungsmethoden in OpenFOAM ein numerisches Modell für das Elektronenstrahlschweißen entwickelt. Es ist in der Lage, die dafür relevanten Einflussfaktoren zu berücksichtigen. So werden die Wärmeübertragung im Feststoff und der Schmelze, alle Aggregatzustandsänderungen und die auf die Dynamik der Schmelze wirkenden Kräfte einbezogen. Das entwickelte Simulationsmodell ist in der Lage zu zeigen, dass außer der natürlichen Konvektion vor allem der beim Verdampfen der Schmelze entstehende Überdruck und die thermokapillare Konvektion an der Schmelzeoberfläche für hohe Strömungsgeschwindigkeiten verantwortlich sind. Darüber hinaus haben neben der Schmelzbaddynamik die thermophysikalischen Eigenschaften des Stahls einen starken Einfluss auf die Ausprägung der Schweißnaht. Vor allem die Wärmeleitfähigkeit verändert diese erheblich, was die Simulationen unter Berücksichtigung der Temperaturabhängigkeit verdeutlichen. Die in dieser Arbeit erreichten Erkenntnisse helfen, die beim Elektronenstrahlschweißen entstehenden Nahtgeometrien und die Gründe für hohe Strömungsgeschwindigkeiten im Schmelzbad besser einordnen und verstehen zu können. Darüber hinaus dient das entwickelte numerische Modell mit der Berücksichtigung aller relevanten Mechanismen als Grundlage für Weiterentwicklungen hinsichtlich vielerlei Anwendungen, beispielsweise für das Schweißen anderer Werkstoffe, zusätzliche Effekte wie dem Spiking oder anderen Elektronenstrahltechnologien wie dem Elektronenstrahlschmelzen im Bereich der additiven Fertigung.