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Due to the unique electronic band structure, graphene has opened the great potential to extend the functionality of a large variety of graphene-based devices in health and environment, energy storage, or various microelectronic applications, to mention a few. At this point, the implementation of graphene into Silicon (Si) semiconductor technology is strongly dependent on several key challenges. Among them, high-quality and wafer-scale graphene synthesis on CMOS compatible substrates is of the highest importance. Though large-area graphene can be achieved on substrates like copper, platinum, silicon carbide, or single-crystal Ni, however, high growth temperatures, unavailability of large scale, or contamination issues are the main drawbacks of their usage. In this PhD work, 8-inch scale graphene synthesis is attempted on alternative substrates such as epitaxial Germanium on Si and polycrystalline Nickel on Si. To achieve the growth of the highest quality of graphene, this work focuses on the investigations of various nucleation and growth mechanisms, substrate–graphene interfaces, effects of different substrate orientations, and detailed microscopic and macroscopic characterization of the grown films. Finally, it should also be stressed that the experiments in this work were carried out in a standard BiCMOS pilot-line, making this study unique, as its results might directly pave the way to further graphene integration and graphene-based device prototyping in mainstream Si technologies.
Determination of specific metabolic activities of anammox bacteria and their sensitivity to oxygen
(2013)
The discovery of Anammox bacteria has bridged our knowledge gap in the nitrogen cycle. This is because it explained the direct conversion of nitrite and ammonium to nitrogen gas in many reducing natural environments. However, it has been found that the presence of oxygen is an important determinat factor for certain biochemical processes and distribution of organisms in the environment. In this work, two methodological approaches were used to investigate the specific metabolic activities of Anammox bacteria and their sensitivity to oxygen using a mixed biomass culture. Two laboratory-scale bioreactors were maintained and the biomass in the reactors served as the inoculum for the investigations. The molecular characterization of the biomass was done using the Fluorescence in situ hybridization (FISH) technique. The specific Anammox activity (SAA) and important inhibition kinetic parameter characterization were estimated while monitoring activities of the biomass using several batch experiments.
The results of the biochemical characterization revealed that several microbial activities such as denitrification, nitrification, dissimilatory nitrate reduction to ammonium and Anammox processes were competing in the bioreactors. These were observed in the analysis of effluent recirculation of the feed solutions in the bioreactors, however, the Anammox process was predominant. An optimum sonication time top of eight minutes was established used to determine the average optical density to dry mass (OD: DM) ratio of 0.87 in the biomass. The FISH characterization estimated 60.4 % ± 14.6% (mean ± standard deviation) Anammox bacteria concentration in the biomass of Bioreactor 1. The Anammox bacteria were made up C. Kuenenia Stuttgartiensis (̴ 78%) and the remaining C. Brocadia Fulgida.
The maximum SAA of 0.025 mgNH4-N (TSSAnammox-1. d-1) and 5.4 mgNH4–N (1011 CellAnammox-1. d-1) for ammonium, and 0.04 mg N2-N (TSSAnammox-1. d-1) and 9.4 mgN2–N (1011 CellAnammox-1. d-1) for nitrogen gas were found in the biomass. While a binding affinity constant Ki = 0.07 mgO2 /l, maximum half inhibition concentration IC50 ̴ 0.2 mg O2 /l and KM = 50 mg/l were estimated for the inhibition kinetics of oxygen in the biomass. The low Ki value found in this study indicates that oxygen is an efficient inhibitor for Anammox activities and concentrations between 0.4 - 0.64 mg O2 /l can lead to complete inhibition of Anammox activity. However, this process is reversible. Finally, the implication of this inhibition kinetic results might be important in tracing the distribution of Anammox processes in natural environments where fixed nitrogen is present.
With the rapid growth of renewable energy sources (RES) in the power generation mix in accordance with the German energy transition policy (‘Energiewende’), fewer baseload coal power plants will be required. Future power generation will be supplied through decentralized power utilities such as off-shore wind parks and also through high operational flexibility of existing conventional coal power units. High operational flexibility means conventional power plants have to increase cyclic operations to cope with feed-ins from variable-RES such as wind and solar.
Unlike medium and peak load power plants that can react quickly to load changes and power ramps, baseload power plants are not suited for such operations. Important technical requirements for flexible operation include among others; frequent start-ups and shut-downs, a minimum downtime, shorter startup time and short operational periods. Baseload coal power plants however do not meet these requirements.
This increased cyclic mode of operation can have severe impacts on vital power plant components such as superheater and reheater tubes resulting in high temperature cyclic oxidation/corrosion especially because these plants were not designed for frequent cyclic operations. To optimize plant operations, minimize material damage and reduce operational and maintenance cost, it is therefore important to understand the oxidation and corrosion risk to plants materials associated with this flexible mode of operation.
In this context, thermochemical modeling in FactSage 6.4ᵀᴹ as well as experimental investigations were carried out. For the experimental investigations, five commercial coal boiler superheater and reheater materials, namely T91, VM12-SHC, TP347-HFG, DMV304 HCu and DMV310 N were exposed for 1000 hours under discontinuous isothermal oxidation conditions and 1000 hours thermo–cyclic oxidation conditions at a metal surface temperature of 650 °C. The synthetic corrosive flue gas consisted of a mixture of CO₂, O₂, SO₂, N₂ and H₂O. The test material samples were partly covered in fly ash to investigate the effect ash deposits on the corrosion and oxidation behavior of the test materials. After exposure metallographic analysis by means of light microscopy and scanning electron microscopy (LOM and SEM–EDS) were carried out to study the oxide morphology and micro–structural properties of the materials. The oxidation kinetics (weight change) results showed significant oxide growth rates (weight gain) under cyclic oxidation conditions especially in the martensitic alloys – T91, VM12-SHC.
Furthermore, metallographic analysis revealed severe oxide spallation in the ash covered sections of these alloys. The austenitic materials (TP374-HFG, DMV310 N) with the exception of DMV304 HCu showed good oxidation behavior with minimal oxide growth both under isothermal and thermal cyclic conditions. However, severe grain boundary attack and internal sulphidation were found in these alloys. DMV310 N showed the best corrosion and oxidation performance. The thermochemical modeling calculations supported the experimental results.
Einige Effekte von Silizium sind bis heute ungeklärt. Dazu zählt Oxidation von hoch-dotiertem n-Si in Fluor-haltigen Säuren im Dunkeln. Diese Oxidation wurde erstmals systematisch untersucht und zur Grundlage eines Modells für Elektroneninjektion gemacht. Die angenommenen Oberflächenkomplexen erklären den Einsatz der Kennlinien. Weitere Untersuchungen zur Identifizierung des Komplexes sowie seiner energetischen Position bieten sich an. Mit zyklischen Voltammogrammen wurde gezeigt, dass die Vorschubgeschwindigkeit des Potentials entscheidend für die Gestalt der Kennlinien ist. Schon 20mV/s ist für das untersuchte System zu schnell, um einen Gleichgewichtszustand zu erreichen. Dies wird durch die Ausbildung von Hysteresen klar erkennbar. Der initielle Strompuls zeigt eine vielfache Stromdichte gegenüber den bekannten Werten der nachfolgenden Oszillationspulse. Die Wasserstoff-terminierte Grenzfläche wird innerhalb weniger Zehntelsekunden oxidiert und passiviert. Alle nachfolgenden Strompulse können als weniger gut synchronisierte Oxidationen verstanden werden.
In this work, growth and characterisation of 3C-SiC thin films, investigation of oxidation of thus prepared layers and Pr-silicate and AlON based interface with SiC have been studied. Chemical vapor deposition of 3C-SiC thin films on Si(001) and Si(111) substrates has been investigated. Prior to the actual SiC growth, preparation of initial buffer layers of SiC was done. Using such a buffer layer, epitaxial growth of 3C-SiC has been achieved on Si(111) and Si(001) substrates. The temperature of 1100°C and 1150°C has been determined to be the optimal temperature for 3C-SiC growth on Si (111) and Si(001) substrates respectively. The oxidation studies on SiC revealed that a slow oxidation process at moderate temperatures in steps was useful in reducing and suppressing the g-C at the SiO2/SiC interface. Clean, graphitefree SiO2 has been successfully grown on 3C-SiC by silicon evaporation and UHV anneal. For the application of high-k Pr2O3 on silicon carbide, plausible interlayer, Pr-Silicate and AlON, have been investigated. Praseodymium silicate has been prepared successfully completely consuming the SiO2 and simultaneously suppressing the graphitic carbon formation. A comparatively more stable interlayer using AlON has been achieved. This interlayer mainly consists of stable phases of AlN along with some amount of Pr-aluminates and CN. Such layers act as a reaction barrier between Pr2O3 and SiC, and simultaneously provide higher band offsets.