Mesoscale optical phenomena occur when light interacts with a number of different types of materials, such as biological and chemical systems and fabricated nanostructures. As a framework, mesoscale optics unifies the interpretations of the interaction of light with complex media when the outcome depends significantly upon the scale of the interaction. Most importantly, it guides the process of designing an optical sensing technique by focusing on the nature and amount of information that can be extracted from a measurement. Different aspects of mesoscale optics are addressed in this dissertation which led to the solution of a number of problems in complex media. Dynamical and structural information from complex fluids—such as colloidal suspensions and biological fluids—was obtained by controlling the size of the interaction volume with low coherence interferometry. With this information, material properties such as particle sizes, optical transport coefficients, and viscoelastic characteristics of polymer solutions and blood were determined in natural, realistic conditions that are inaccessible to conventional techniques. The same framework also enabled the development of new, scale-dependent models for several important physical and biological systems. These models were then used to explain the results of some unique measurements. For example, the transport of light in disordered photonic lattices was interpreted as a scale-dependent, diffusive process to explain the anomalous behavior of photon path length distributions through these complex structures. In addition, it was demonstrated how specialized optical measurements and models at the mesoscale enable solutions to fundamental problems in cell biology. Specifically, it was found for the first time that the nature of cell motility changes markedly with the curvature of the substrate that the cells iv move on. This particular work addresses increasingly important questions concerning the nature of cellular responses to external forces and the mechanical properties of their local environment. Besides sensing of properties and modeling behaviors of complex systems, mesoscale optics encompasses the control of material systems as a result of the light-matter interaction. Specific modifications to a material’s structure can occur due to not only an exchange of energy between radiation and a material, but also due to a transfer of momentum. Based on the mechanical action of multiply scattered light on colloidal particles, an optically-controlled active medium that did not require specially tailored particles was demonstrated for the first time. The coupling between the particles and the random electromagnetic field affords new possibilities for controlling mesoscale systems and observing nonequilibrium thermodynamic phenomena

In the Manufacturing Industry there is a subset of technologies referred to as Rapid Technologies which are those technologies that create the ability to compress the time to market for new products under development . Of this subset, Additive Fabrication (AF), or more commonly known as Rapid Prototyping (RP), acquires much attention due to its unique and futuristic approach to the production of physical parts directly from 3D CAD data, CT or MRI scans, or data from laser scanning systems by utilizing various techniques to consecutively generate cross-sectional layers of a given thickness upon the previous layer to form 3D objects. While Rapid Prototyping is the most common name for the production technology it is also referred to as Additive Manufacturing, Layer Based Manufacturing, Direct Digital Manufacturing, Free-Form Fabrication, and 3-Dimensional Printing. With over 35 manufacturers of Additive Fabrication equipment in 2006 , the selection of an AF process and material for a specific application can become a significant task, especially for those with little or no technical experience with the technology and to add to this challenge, many of the various processes have multiple material options to select from . This research was carried out in order to design and construct a system that would allow a person, regardless of their level of technical knowledge, to quickly and easily filter through the large number of Additive Fabrication processes and their associated materials in order to find the most appropriate processes and material options to create physical reproductions of any part. The selection methodology used in this paper is a collection of assumptions and rules taken from the author's viewpoint of how, in real world terms, the selection process generally takes place between a consumer and a service provider. The methodology uses those assumptions in conjunction with a set of expert based rules to direct the user to a best set of qualifying processes and materials suited for their application based on as many or as few input fields the user may be able to complete.

Batteries are increasingly seen as an indispensable element in the rapid progress of the energy transition. With forecasts for global demand set to reach 2 TWh by 2030 and increasing policy support for battery manufacturers, many questions arise on whether the current rapid expansion of battery manufacturing industry is sustainable. Issues regarding the stability of the supply chain and rising energy security concerns has led to an expanded focus on alternate battery technologies. Sodium ion cells are commonly cited as a potential solution to many of the current issues facing the lithium-ion battery industry. With sodium ion cells reaching commercialization, this thesis would like to explore the viability of commercial sodium ion cells through a bottom-up manufacturing and regional cost analysis of Sodium Prussian Blue Analogues and Sodium Layered Oxides. To account for the more qualitative aspects of regional battery manufacturing, the current policy framework and supply chain are briefly explored. To study the current commercial sodium ion cells, the report considers Na0.9[Cu0.22Fe0.30Mn0.48] O2 (Na Oxide) and Na2MnFe(CN)6 (Na PBA) cathode chemistries which are similar to the cells manufactured by HiNa and Novasis Energies respectively. These cells are compared to two of the most common Lithium chemistries on the market, LiFePO4 (LFP) and LiNi0.3Mn0.3Co0.3 (Li NMC111). Various manufacturing scales of the model plant are explored for each chemistry, and the changes in manufacturing costs for the US, China, India, Sweden and Chile are explored. Considering a baseline plant of 1500 MWh/yr, the base case results show that from the cost perspective the sodium ion cells are not too different from that of the lithium-ion cells. The cost of the lithium ion cells NMC111 and LFP (2019 US$) are at 126 $/kWh and 113$/kWh while the Na Oxide and Na PBA cell costs are at 125 $/kWh and 148 $/kWh. While the costs are comparable, the volumetric energy density of the sodium cells is almost half that of their lithium counterparts, which hampers the overall cost advantage from the cheaper materials. Compared to the lithium cells where the cathode and anode are on average the most expensive components, the separator and the hard carbon anode become the most expensive cost components in the sodium ion cells studied. In the regional analysis, China and Chile have the cheapest cell costs for both sodium and lithium, while the US and India are the most expensive within the countries studied with the maximum cost difference in the range of 15 $/kWh. While most countries have differing approaches in terms of policy support, the trend towards domestic sourcing of supplies can clearly be seen in most of the countries studied. The past three years has seen interest in battery manufacturing escalate significantly, with slow policy support in the 2010s from most countries. Chile is a notable exception with a lack of strong policy support. For the manufacturing scale, it was found that the minimum effective scale was 1500 MWh annually. The capital costs for the sodium ion cell plants were 16% more expensive than the lithium cell plants due to increased production rates to meet the same annual production. With cathode thickness, it was found that the Na PBA cell benefited the most with the increase in thickness, as it had the highest CAM capacity. The cost advantages of the sodium ion cells start to materialise when considering the increase in price of materials in 2022. When considering increased metal costs in 2022, the price of the Li NMC and LFP cells increase to around 186 $/kWh, while sodium ion cells don’t display an appreciable change in cost. Furthermore, when considering a higher power rate of 5C, the lithium cells perform poorly with Li NMC increasing to 188 $/kWh and LFP to 148 $/kWh while the sodium cells remain close to their 0.2C costs at 148$/kWh for Na PBA and 127 $/kWh for Na Oxide. / Batterier betraktas i allt högre grad som en oumbärlig komponent i den snabba utvecklingen av energiomställningen. Med prognoser som visar att den globala efterfrågan kommer att nå 2 TWh år 2030, och med ökat stöd från myndigheter till batteritillverkare, uppstår många frågor om huruvida den nuvarande snabba expansionen av batteritillverkningsindustrin är hållbar. Frågor om stabiliteten i leveranskedjan och ökad oro för energisäkerheten har lett till ett ökat fokus på alternativa batteriteknologier. Natriumjonceller nämns ofta som en potentiell lösning på många av de aktuella problemen som litiumjonbatteriindustrin står inför. Denna avhandling syftar till att undersöka livsdugligheten hos kommersiella natriumjonceller genom en bottom-up-tillverkning och regional kostnadsanalys av natriumpreussiska blåanaloger och natriumskiktade oxider. För att belysa de mer kvalitativa aspekterna av regional batteritillverkning undersöks även den nuvarande politiska ramen och leveranskedjan kortfattat. För att studera de nuvarande kommersiella natriumjoncellerna överväger rapporten katodkemin Na0.9[Cu0.22Fe0.30Mn0.48]O2 (Na Oxide) och Na2MnFe(CN)6 (Na PBA), som liknar celler som tillverkas av HiNa respektive Novasis Energies. Dessa celler jämförs med två av de vanligaste litiumkemikalierna på marknaden, LiFePO4 (LFP) och LiNi0.3Mn0.3Co0.3 (Li NMC111). Olika tillverkningsskalor i modellfabriker undersöks för varje kemikalie, och förändringarna i tillverkningskostnaderna i USA, Kina, Indien, Sverige och Chile analyseras. Med en baslinjeanläggning på 1500 MWh/år visar basfallsresultaten att natriumjoncellerna inte skiljer sig alltför mycket kostnadsmässigt från litiumjoncellerna. Kostnaden för litiumjoncellerna NMC111 och LFP är 126 $/kWh respektive 113 $/kWh, medan kostnaderna för Na Oxide och Na PBA-celler ligger på 125 $/kWh respektive 148 $/kWh. Trots att kostnaderna är jämförbara är natriumcellernas volymetriska energitäthet nästan hälften så stor som deras litiumequivalenter, vilket minskar den totala kostnadsfördelen av de billigare materialen. Jämfört med litiumcellerna, där katoden och anoden i genomsnitt utgör de dyraste komponenterna, är separatorn och hårdkolanoden de dyraste kostnadskomponenterna i de undersökta natriumjoncellerna. I den regionala analysen har Kina och Chile de lägsta cellkostnaderna för både natrium och litium, medan USA och Indien är dyrast bland de undersökta länderna med en maximal kostnadsskillnad på 15 $/kWh. Även om de flesta länder har olika tillvägagångssätt när det gäller politiskt stöd, kan trenden mot inhemska inköp av material tydligt ses i de flesta av de undersökta länderna. Under de senaste tre åren har intresset för batteritillverkning ökat betydligt, efter ett långsamt politiskt stöd under 2010-talet från de flesta länder. Chile utgör ett anmärkningsvärt undantag med brist på starkt politiskt stöd. Vid tillverkningsskalan fann man att den lägsta effektiva skalan var 1500 MWh årligen. Kapitalkostnaderna för natriumjoncellsanläggningar var 16 % dyrare än för litiumjoncellsanläggningar på grund av ökade produktionshastigheter för att uppnå samma årsproduktion. När det gäller katoddjocklek så gynnades Na PBA-cellen mest av en ökning i tjocklek, eftersom den hade den högsta CAM-kapaciteten. Fördelarna med natriumjonceller börjar realiseras när man beaktar prisökningen på material år 2022. Vid en ökning av metallkostnaderna 2022 ökar priset på Li NMC- och LFP-cellerna till cirka 186 $/kWh, medan kostnaden för natriumjoncellerna inte uppvisar någon märkbar förändring. Dessutom, vid en högre effekt på 5C, presterar litiumcellerna dåligt med en kostnad på 188 $/kWh för Li NMC och 148 $/kWh för LFP, medan kostnaden för natriumcellerna förblir nära deras kostnader vid 0,2C, nämligen 148 $/kWh för Na PBA och 127 $/kWh för Na Oxide.

Monolayer two-dimensional (2D) materials have been regarded as a hot topic in the fields of condensed matter physics, materials science, and chemistry due to their unique physical, chemical, and electronic properties. However, the research on the preparation method and properties understanding of the 2D monolayer are inadequate. In this dissertation, taking 2D nickel-iron layered double hydroxides (NiFe LDHs) and molybdenum disulfide (MoS2) as examples, the practicability of the direct synthesis of NiFe LDHs monolayer and the thermal enhancement catalytic performance of 2D MoS2 monolayer (MoS2 ML) are discussed. First, a one-pot synthetic strategy (bottom-up method) is presented to synthesize 2D NiFe-based LDHs monolayers, including NiFe, Co-, Ru-, doped, and Au-modified NiFe LDHs. The prerequisite and universality of this strategy are investigated and confirmed. The features of LDHs are characterized by advanced technologies. The obtained LDH bulks own a large interlayer spacing up to 8.2 Å, which can be facilely exfoliated into monolayers in water by hand-shaking within 10 s. As a result, the as-prepared NiFe-based LDH monolayers display a good electrocatalytic oxygen evolution reaction (OER) performance. This facile strategy paves the way for designing easily exfoliated LDHs for highly active catalysts and energy conversion devices based on other monolayer LDHs. Second, with gold-modified tape, 2D MoS2 ML is exfoliated from the bulk crystal through a micromechanical exfoliation method (top-down strategy). The thermal effects of MoS2 ML are confirmed by Raman and photoluminescence (PL) spectra. Moreover, an on-chip MoS2 ML hydrogen evolution reaction (HER) reactor is designed and fabricated. The thermal effects generate efficient electron transfer in the MoS2 ML and at the electrolyte-catalyst (MoS2 ML) interface, leading to an enhanced HER performance. Compared to the results obtained at room temperature, the MoS2 ML shows a direct thermal enhanced HER performance at higher temperatures. In summary, the findings and understandings, the direct synthesis and direct thermal enhancement catalytic performance, of 2D monolayers offer a guideline for synthesizing and catalyst application of other 2D monolayers.

An experimental investigation of an M level (M = 16, 64 and 256) Quadrature Amplitude Modulation (QAM) transmission system suitable for video transmission is presented. The communication system is based on layered video coding and unequal error protection to make the video bitstream robust to channel errors. An implementation is described in which H.264 video is protected unequally by partitioning the compressed data into two layers of different visual importance. The partition scheme is based on a separation of the group of pictures (GoP) in the intra-coded frame (I-frame) and predictive coded frame (P frame). This partition scheme is then applied to split the H.264-coded video bitstream and is suitable for Constant Bit Rate (CBR) transmission. Unequal error protection is based on uniform and non-uniform M-QAM constellations in conjunction with different scenarios of splitting the transmitted symbol for protection of the more important information of the video data; different constellation arrangements are proposed and evaluated to increase the capacity of the high priority layer. The performance of the transmission system is evaluated under Additive White Gaussian Noise (AWGN) and Rayleigh fading conditions. Simulation results showed that in noisy channels the decoded video can be improved by assigning a larger portion of the video data to the enhancement layer in conjunction with non-uniform constellation arrangements; in better channel conditions the quality of the received video can be improved by assigning more bits in the high priority channel and using uniform constellations. The aforementioned varying conditions can make the video transmission more successful over error-prone channels. Further techniques were developed to combat various channel impairments by considering channel coding methods suitable for layered video coding applications. It is shown that a combination of non-uniform M-QAM and forward error correction (FEC) will yield a better performance. Additionally, antenna diversity techniques are examined and introduced to the transmission system that can offer a significant improvement in the quality of service of mobile video communication systems in environments that can be modelled by a Rayleigh fading channel.

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In this work, the crystal growth as well as structural and magnetic investigations of several metal trichalcogenides compounds with a general formula M2X2Ch6 are presented. M stands for a main group metal or transition metal, X is an element of the IV or V main group and Ch is a chalcogen. In particular, these compounds are the phosphorus sulfides Fe2P2S6, Ni2P2S6 as well as intermediate compounds of the substitution regime (Fe1-xNix)2P2S6, the quarternary phosphorus sulfides CuCrP2S6 and AgCrP2S6 and the germanium tellurides Cr2Ge2Te6 and In2Ge2Te6. As members of the metal trichalcogenides, all these compounds have a van der Waals layered honeycomb structure in common. This layered structure in combination with their magnetic properties makes these compounds interesting candidate materials for the production of magnetic monolayers by exfoliation from bulk crystals. Crystals of the phosphorus sulfides were grown by the chemical vapor transport technique and, for the growth of the germanium tellurides, the self-flux growth technique was used. Crystals of all phases were extensively characterized regarding their morphology, chemical composition and homogeneity as well as regarding their crystal structure. The structural analysis, especially for Ni2P2S6, yields insight into details of the stacking order and disorder of the corresponding quasi-two-dimensional layers in the bulk. Regarding the magnetic properties, both Fe2P2S6 and Ni2P2S6 order antiferromagnetically but exhibit different magnetic anisotropies (i.e. Ising-like anisotropy for Fe2P2S6 and XYZ anisotropy for Ni2P2S6). In this context, it is surprising to find that compounds in the solid solution regime of (Fe1-xNix)2P2S6 up to x = 0.9 exhibit an anisotropic magnetic behavior that is comparable to Fe2P2S6 and, thus, indicative of Ising-like anisotropy. For CuCrP2S6 and AgCrP2S6, the ordering of the two different transition elements on the honeycomb sites yields more complex magnetic structures. The magnetic Cr3+ atoms in CuCrP2S6 order in a triangular arrangement and form an antiferromagnetic ground state with notable ferromagnetic interactions. AgCrP2S6 exhibits pronounced features of low dimensional magnetism resulting from the (quasi-)one-dimensional stripe-like arrangement of magnetic Cr3+ atoms and no onset of long-range magnetic order is unambiguously observed. Cr2Ge2Te6 exhibits ferromagnetic order and an anisotropic feature in the temperature dependence of the magnetization. Based on the magnetic phase diagrams for two orientations between the magnetic field and the crystallographic directions, the temperature dependence of the magnetocrystalline anisotropy constant as well as the critical exponents of the magnetic phase transition are extracted. Concluding from this, the magnetic interactions in Cr2Ge2Te6 are dominantly of two-dimensional nature and the anisotropy is uniaxial with the before mentioned anisotropic feature resulting from the interplay between magnetocrystalline anisotropy, magnetic field, and temperature. In2Ge2Te6 is diamagnetic as to be expected for a closed-shell system. Additional to the investigations on single crystals, the quasi-binary phase diagram of (Cu1-xAgx)CrP2S6 was investigated for regimes of solid solution behavior based on polycrystalline samples. Accordingly, isostructural substitution is most likely possible in the composition range of (Cu0.25Ag0.75)CrP2S6 to AgCrP2S6, potentially allowing to tune the magnetic interactions of the Cr sublattice indirectly by substitution on the Cu/Ag sublattice.:1. Introduction 1.1. M2X2Ch6 Class of Materials 1.2. Magnetism in Solid State Materials 1.2.1. Diamagnetism 1.2.2. Paramagnetism 1.2.3. Cooperative Magnetism 1.2.4. Magnetic Anisotropy 1.2.5. Magnetism in D < 3 1.2.6. Critical Exponents 2. Methods 2.1. Synthesis and Crystal Growth 2.1.1. Solid State Synthesis 2.1.2. Crystal Growth via the Liquid Phase 2.1.3. Crystal Growth via the Vapor Phase 2.2. X-ray Diffraction 2.2.1. Single Crystal X-ray Diffraction 2.2.2. Powder X-ray Diffraction 2.3. Scanning Electron Microscopy and Energy Dispersive X-ray Spectroscopy 2.3.1. Scanning Electron Microscopy 2.3.2. Energy Dispersive X-ray Spectroscopy 2.4. Magnetometry 2.5. Nuclear Magnetic Resonance Spectroscopy 2.6. Specific Heat Capacity 3. M2P2S6 3.1. Ni2P2S6 3.1.1. Crystal Growth 3.1.2. Characterization 3.1.3. Magnetic Properties 3.1.4. 31P-NMR Spectroscopy 3.1.5. Stacking (Dis-)Order in Ni2P2S6 3.2. (Fe1-xNix)2P2S6 3.2.1. Synthesis and Crystal Growth 3.2.2. Characterization 3.2.3. Evolution of Magnetic Properties 3.3. Summary and Outlook 4. M1+CrP2S6 4.1. CuCrP2S6 4.1.1. Crystal Growth 4.1.2. Characterization 4.1.3. Magnetic Properties 4.2. AgCrP2S6 4.2.1. Crystal Growth 4.2.2. Characterization 4.2.3. Magnetic Properties 4.3. Polycrystalline (Cu1-xAgx)CrP2S6 4.3.1. Synthesis 4.3.2. Phase Analysis 4.4. Summary and Outlook 5. M2(Ge,Si)2Te6 5.1. Cr2Ge2Te6 5.1.1. Crystal Growth 5.1.2. Characterization 5.1.3. Magnetic Properties 5.1.4. Analysis of the Critical Behavior 5.2. In2Ge2Te6 5.2.1. Crystal Growth 5.2.2. Characterization 5.2.3. Magnetic Properties 5.2.4. Specific Heat 5.3. Summary and Outlook 6. Conclusion Bibliography List of Publications Acknowledgements Eidesstattliche Erklärung A. Appendix A.1. Scanning Electron Microscopic Images A.1.1. (Fe1-xNix)2P2S6 A.2. scXRD A.2.1. (Fe1-xNix)2P2S6 / In dieser Arbeit werden die Kristallzüchtung sowie strukturelle und magnetische Untersuchungen an mehreren Metalltrichalkogenid-Verbindungen mit der allgemeinen Summenformel M2X2Ch6 vorgestellt. M steht für ein Hauptgruppen- oder Übergangsmetall, X ist ein Element der IV- oder V-Hauptgruppe und Ch ein Chalkogen. Insbesondere handelt es sich bei diesen Verbindungen um die Phosphorsulfide Fe2P2S6, Ni2P2S6 sowie um Verbindungen der Substitutionsreihe (Fe1-xNix)2P2S6, die quaternären Phosphorsulfide CuCrP2S6 und AgCrP2S6 sowie die Germaniumtelluride Cr2Ge2Te6 und In2Ge2Te6. Als Mitglieder der Metalltrichalkogenide haben alle diese Verbindungen eine van-der-Waals-Schichtstruktur mit Honigwabenmotiv gemein. Diese Schichtstruktur in Kombination mit ihren magnetischen Eigenschaften macht diese Verbindungen zu interessanten Kandidaten für die Herstellung von magnetischen Monolagen durch Exfoliation aus Volumenkristallen. Kristalle der Phosphorsulfide wurden mit der chemischen Dampfphasentransporttechnik gezüchtet und für die Züchtung der Germaniumtelluride wurde die Selbstflusstechnik verwendet. Die Kristalle aller Phasen wurden sowohl hinsichtlich ihrer Morphologie, chemischen Zusammensetzung und Homogenität als auch hinsichtlich ihrer Kristallstruktur umfassend charakterisiert. Die Strukturanalyse, insbesondere für Ni2P2S6, gibt Aufschluss über Details der Stapelordnung und -unordnung der entsprechenden quasizweidimensionalen Schichten im Volumen. Bezüglich der magnetischen Eigenschaften ordnen sowohl Fe2P2S6 als auch Ni2P2S6 antiferromagnetisch, zeigen aber unterschiedliche magnetische Anisotropien (d.h. Ising-artige Anisotropie für Fe2P2S6 und XYZ-Anisotropie für Ni2P2S6). In diesem Zusammenhang ist es überraschend, dass Verbindungen im Mischkristallregime von (Fe1-xNix)2P2S6 bis x = 0.9 ein anisotropes magnetisches Verhalten zeigen, das mit dem von Fe2P2S6 vergleichbar ist und daher auf Ising-artige Anisotropie hindeutet. Bei CuCrP2S6 und AgCrP2S6 führt die Anordnung der beiden unterschiedlichen Übergangselemente auf den Gitterplätzen der Wabenstruktur zu komplexeren magnetischen Strukturen. Die magnetischen Cr3+ Atome in CuCrP2S6 ordnen sich in einer Dreiecksanordnung an und bilden einen antiferromagnetischen Grundzustand mit ausgeprägten ferromagnetischen Wechselwirkungen. AgCrP2S6 weist deutliche Merkmale von niederdimensionalem Magnetismus auf, welche aus der (quasi-)eindimensionalen, streifenartigen Anordnung der magnetischen Cr3+ Atome resultieren, und das Einsetzen von langreichweitiger magnetischer Ordnung kann nicht eindeutig beobachtet werden. Cr2Ge2Te6 weist ferromagnetische Ordnung und einen anisotropen Verlauf der Temperaturabhängigkeit der Magnetisierung auf. Anhand von magnetischen Phasendiagrammen für zwei Orientierungen zwischen Magnetfeld und kristallographischen Richtungen wurden die Temperaturabhängigkeit der magnetokristallinen Anisotropiekonstante sowie die kritischen Exponenten des magnetischen Phasenübergangs extrahiert. Hieraus ergibt sich, dass die magnetischen Wechselwirkungen in Cr2Ge2Te6 überwiegend zweidimensionaler Natur sind und die Anisotropie uniaxial ist, wobei der zuvor erwähnte anisotrope Verlauf aus dem Zusammenspiel von magnetokristalliner Anisotropie, Magnetfeld und Temperatur resultiert. In2Ge2Te6 ist diamagnetisch, wie es für ein System mit geschlossener Schale zu erwarten ist. Zusätzlich zu den Untersuchungen an Einkristallen wurde das quasibinäre Phasendiagramm von (Cu1-xAgx)CrP2S6 anhand von polykristallinen Proben auf Bereiche mit Mischkristallverhalten hin untersucht. Folglich ist eine isostrukturelle Substitution höchstwahrscheinlich im Zusammensetzungsbereich von (Cu0.25Ag0.75)CrP2S6 bis AgCrP2S6 möglich, was es erlauben könnte, die magnetischen Wechselwirkungen des Cr-Untergitters indirekt durch Substitution auf dem Cu/Ag-Untergitter zu beeinflussen.:1. Introduction 1.1. M2X2Ch6 Class of Materials 1.2. Magnetism in Solid State Materials 1.2.1. Diamagnetism 1.2.2. Paramagnetism 1.2.3. Cooperative Magnetism 1.2.4. Magnetic Anisotropy 1.2.5. Magnetism in D < 3 1.2.6. Critical Exponents 2. Methods 2.1. Synthesis and Crystal Growth 2.1.1. Solid State Synthesis 2.1.2. Crystal Growth via the Liquid Phase 2.1.3. Crystal Growth via the Vapor Phase 2.2. X-ray Diffraction 2.2.1. Single Crystal X-ray Diffraction 2.2.2. Powder X-ray Diffraction 2.3. Scanning Electron Microscopy and Energy Dispersive X-ray Spectroscopy 2.3.1. Scanning Electron Microscopy 2.3.2. Energy Dispersive X-ray Spectroscopy 2.4. Magnetometry 2.5. Nuclear Magnetic Resonance Spectroscopy 2.6. Specific Heat Capacity 3. M2P2S6 3.1. Ni2P2S6 3.1.1. Crystal Growth 3.1.2. Characterization 3.1.3. Magnetic Properties 3.1.4. 31P-NMR Spectroscopy 3.1.5. Stacking (Dis-)Order in Ni2P2S6 3.2. (Fe1-xNix)2P2S6 3.2.1. Synthesis and Crystal Growth 3.2.2. Characterization 3.2.3. Evolution of Magnetic Properties 3.3. Summary and Outlook 4. M1+CrP2S6 4.1. CuCrP2S6 4.1.1. Crystal Growth 4.1.2. Characterization 4.1.3. Magnetic Properties 4.2. AgCrP2S6 4.2.1. Crystal Growth 4.2.2. Characterization 4.2.3. Magnetic Properties 4.3. Polycrystalline (Cu1-xAgx)CrP2S6 4.3.1. Synthesis 4.3.2. Phase Analysis 4.4. Summary and Outlook 5. M2(Ge,Si)2Te6 5.1. Cr2Ge2Te6 5.1.1. Crystal Growth 5.1.2. Characterization 5.1.3. Magnetic Properties 5.1.4. Analysis of the Critical Behavior 5.2. In2Ge2Te6 5.2.1. Crystal Growth 5.2.2. Characterization 5.2.3. Magnetic Properties 5.2.4. Specific Heat 5.3. Summary and Outlook 6. Conclusion Bibliography List of Publications Acknowledgements Eidesstattliche Erklärung A. Appendix A.1. Scanning Electron Microscopic Images A.1.1. (Fe1-xNix)2P2S6 A.2. scXRD A.2.1. (Fe1-xNix)2P2S6

<p>This thesis is concerned with a theoretical and experimental investigation of a duckbill valve (DBV). Duckbill valves are non-return valves made of a composite material, which deforms to open the valve as the upstream pressure increases. The head-discharge behavior is a fluid-structure interaction (FSI) problem since the discharge depends on the valve opening that in turn depends on the pressure distribution along the valve produced by the discharge. To design a duckbill valve, a theoretical model is required, which will predict the head-discharge characteristics as a function of the fluid flow through the valve and the valve material and geometry.</p> <p>The particular valves of concern in this study, which can be very large, are made from laminated, fiber-reinforced rubber. Thus, the structural problem has strong material as well as geometric nonlinearities due to large deflections. Clearly, a fully coupled FSI analysis using three-dimensional viscous flow would be very challenging and therefore, a simplified approach was sought that treats the essential aspects of the problem in a tractable way. For this purpose, the DBV was modeled using thick shell finite elements, which included the laminates of hyperelastic rubber and orthotropic fabric reinforcement. The finite element method (FEM) was simplified by assuming that the arch side edges of the valve were clamped. The unsteady 1D flow equation was used to model the ideal fluid dynamics that enabled a full FSI analysis. Moreover, verification for the ideal flow was carried out using a transient, Reynolds-averaged Navier-Stokes finite volume solver for the viscous flow corresponding to the deformed valve predicted by the simplified FSI model.</p> <p>In order to validate the predictions of the FSI simulations, an experimental study was performed at several mass flow rates. Pressure drops along the water tunnel, valve inlet and outlet velocity profiles were measured, as well as valve opening deformations as functions of upstream pressures.</p> <p>Additionally, the valve deformations under various back pressures were analyzed when the downstream pressure exceeded the upstream pressure using the layered shell model without coupling and with simplified boundary constraints to avoid solving the contact problem for the inward-deformed duckbill valve. Flow-induced vibration (FIV) of the valve at small openings was also examined to improve our understanding of the valve stability behaviour. Some interesting valve oscillation phenomena were observed.</p> <p>Conclusions are drawn regarding the FSI model on the predictions and comparisons with the experimental results. The transient 1D flow equation has been demonstrated to adequately model the fluid dynamics of a duckbill valve, largely due to the fact that viscous effects are negligible except when the valve is operating at very small openings. Fiber reinforcement of the layered composite rubber was found to play an important role in controlling duckbill valve material stretch, especially at large openings. The model predicts oscillations at small openings but more research is required to better understand this behaviour.</p> / Doctor of Philosophy (PhD)

Topological insulators (TIs) are semiconductors with protected electronic surface states that allow dissipation-free transport. TIs are envisioned as ideal materials for spintronics and quantum computing. In Bi14Rh3I9, the first weak 3D TI, topology presumably arises from stacking of the intermetallic [(Bi4Rh)3I]2þ layers, which are predicted to be 2D TIs and to possess protected edge-states, separated by topologically trivial [Bi2I8]2+ octahedra chains. In the new layered salt Bi12Rh3Cu2I5, the same intermetallic layers are separated by planar, i.e., only one atom thick, [Cu2I4]2- anions. Density functional theory (DFT)-based calculations show that the compound is a weak 3D TI, characterized by Z2 ¼ ð0; 0001Þ, and that the topological gap is generated by strong spin–orbit coupling (Eg,calc.~ 10 meV). According to a bonding analysis, the copper cations prevent strong coupling between the TI layers. The calculated surface spectral function for a finite-slab geometry shows distinct characteristics for the two terminations of the main crystal faces 〈001〉, viz., [(Bi4Rh)3I]2þ and [Cu2I4]2-. Photoelectron spectroscopy data confirm the calculated band structure. In situ four-point probe measurements indicate a highly anisotropic bulk semiconductor (Eg,exp.¼ 28 meV) with pathindependent metallic conductivity restricted to the surface as well as temperatureindependent conductivity below 60 K.

La caractérisation géochimique et isotopique des eaux souterraines de la « zone minéralisée de l’Entre-Deux-Mers » indique une origine commune de la minéralisation, directement liée à la minéralogie des formations captées par les forages.La géochimie montre que les interactions eau-roche sont majoritairement influencées par la présence d’évaporites, mais que d’autres interactions mettant en jeu des carbonates, des silicates et des argiles existent. Un modèle géochimique d’acquisition de la minéralisation reconstitue parfaitement la chimie des eaux souterraines à l’échelle de la zone d’étude. Ce modèle, construit en se basant sur la géochimie des eaux et sur la minéralogie des formations tertiaires du nord du Bassin aquitain, met à l’équilibre des eaux avec des formations carbonatées et évaporitiques. Afin de mieux comprendre la distribution latérale et verticale des formations tertiaires et leur minéralogie, une approche paléogéographique et sédimentologique a permis de localiser les différents horizons riches en sulfates et/ou en fluorures, mais aussi de comprendre leur origine de dépôt. En se basant sur l’hydrogéologie, la paléogéographie, la minéralogie et la géochimie, des hypothèses de répartition de la minéralisation à l’échelle du forage ont pu être testées. Les résultats de la modélisation couplée hydrodynamique–transport reconstituent la chimie des eaux prélevées par les forages de la « zone minéralisée de l’Entre-Deux-Mers ». Au vu de ces résultats, un modèle avec obturation des horizons riches en sulfates et en fluorures a été testé et les résultats obtenus ouvrent des perspectives pour des futures recherches. Ce travail a donc permis de comprendre l’origine de la minéralisation des eaux de « la zone minéralisée de l’Entre-Deux-Mers », mais aussi de proposer des améliorations et des perspectives pour une meilleure gestion d’une des principales ressources en eau potable de la Gironde. / Geochemical and isotopic characterizations of groundwaters in the "mineralized Entre-Deux-Mers area" indicate a common origin of the mineralization, directly linked to the mineralogy of the formations abstracted by drilling.Geochemistry shows that water-rock interactions are mainly influenced by the presence of evaporites, and that but that other interactions involving carbonates, silicates and clays exist. A geochemical model based on the water geochemistry and mineralogy of the Tertiary formations of northern Aquitaine Basin fix waters in equilibrium with evaporitic and carbonated formations. This model reconstitutes perfectly the groundwaters’ chemistry across the study area and explains the mineralization acquisition. Improving the understanding of the lateral and vertical distribution of tertiary formations and their mineralogy requires a sedimentological and paleogeographical approach. This approach allowed to locate the different layers rich in sulphates and/or fluoride and to understand also their origin.Based on hydrogeology, paleogeography, mineralogy and geochemistry, the distribution of the mineralization has been tested at the borehole scale. The results of this coupled hydrodynamic-transport modeling reconstitute the chemistry of the groundwaters in the "mineralized Entre-Deux-Mers area." A model, that considers the sealing of sulphates- and fluorides-rich layers has been tested and its results highlights future research perspectives. This work has allowed understanding the origin of the mineralization of the waters "of the mineralized Entre-Deux-Mers area" and also suggests improvements and prospects for sustainable management of a major drinking water resource in Gironde.