Characterization of Selected Photonic Materials and Systems Using Photoacoustic Technique

The photoacoustic investigations carried out on different photonic materials are presented in this thesis. Photonic materials selected for the investigation are tape cast ceramics, muItilayer dielectric coatings, organic dye doped PVA films and PMMA matrix doped with dye mixtures. The studies are performed by the measurement of photoacoustic signal generated as a result of modulated cw laser irradiation of samples. The gas-microphone scheme is employed for the detection of photoacoustic signal. The different measurements reported here reveal the adaptability and utility of the PA technique for the characterization of photonic materials.Ceramics find applications in the field of microelectronics industry. Tape cast ceramics are the building blocks of many electronic components and certain ceramic tapes are used as thermal barriers. The thermal parameters of these tapes will not be the same as that of thin films of the same materials. Parameters are influenced by the presence of foreign bodies in the matrix and the sample preparation technique. Measurements are done on ceramic tapes of Zirconia, Zirconia-Alumina combination, barium titanate, barium tin titanate, silicon carbide, lead zirconate titanateil'Z'T) and lead magnesium niobate titanate(PMNPT). Various configurations viz. heat reflection geometry and heat transmission geometry of the photoacoustic technique have been used for the evaluation of different thermal parameters of the sample. Heat reflection geometry of the PA cell has been used for the evaluation of thermal effusivity and heat transmission geometry has been made use of in the evaluation of thermal diffusivity. From the thermal diffusivity and thermal effusivity values, thermal conductivity is also calculated. The calculated values are nearly the same as the values reported for pure materials. This shows the feasibility of photoacoustic technique for the thermal characterization of ceramic tapes.Organic dyes find applications as holographic recording medium and as active media for laser operations. Knowledge of the photochemical stability of the material is essential if it has to be used tor any of these applications. Mixing one dye with another can change the properties of the resulting system. Through careful mixing of the dyes in appropriate proportions and incorporating them in polymer matrices, media of required stability can be prepared. Investigations are carried out on Rhodamine 6GRhodamine B mixture doped PMMA samples. Addition of RhB in small amounts is found to stabilize Rh6G against photodegradation and addition of Rh6G into RhB increases the photosensitivity of the latter. The PA technique has been successfully employed for the monitoring of dye mixture doped PMMA sample. The same technique has been used for the monitoring of photodegradation ofa laser dye, cresyl violet doped polyvinyl alcohol also.Another important application of photoacoustic technique is in nondestructive evaluation of layered samples. Depth profiling capability of PA technique has been used for the non-destructive testing of multilayer dielectric films, which are highly reflecting in the wavelength range selected for investigations. Eventhough calculation of thickness of the film is not possible, number of layers present in the system can be found out using PA technique. The phase plot has clear step like discontinuities, the number of which coincides with the number of layers present in the multilayer stack. This shows the sensitivity of PA signal phase to boundaries in a layered structure. This aspect of PA signal can be utilized in non-destructive depth profiling of reflecting samples and for the identification of defects in layered structures.

Thermal diffusivity measurements in organic liquids using transient thermal lens calorimetry

Thermal diffusivity measurements are carried out in certain organic liquids using the pulsed dual beam thermal lens technique. The 532 nm pulses from a frequency doubled Q-switched Nd:YAG laser are used as the heating source and an intensity stabilized He-Ne laser serves as the probe beam. Experimental determination of the characteristic time constant of the transient thermal lens signal is verified theoretically. Measured thermal diffusivity values are in excellent agreement with literature values.

Thermal characterization of ceramic tapes using photoacoustic effect

Thermal characterization of alumina–zirconia and zirconia ceramic tapes using a photoacoustic technique is presented. A transmission-mode geometry is employed for the measurement of thermal diffusivity while a reflection-mode geometry is used for the measurement of thermal effusivity. In both these geometries, the same open photoacoustic cell is used. From the measured values of thermal diffusivity and thermal effusivity, the thermal conductivity value has also been evaluated.

Photothermal Characterization of Nanogold Under Conditions of Resonant Excitation and Energy Transfer

We have performed thermal diffusion measurements of nanofluid containing gold and rhodamine 6G dye in various ratios. At certain concentrations, gold is nearly four times more efficient than water in dissipating small temperature fluctuations in a medium, and therefore it will find applications as heat transfer fluids. We have employed dual-beam mode-matched thermal lens technique for the present investigation. It is a sensitive technique in measuring photothermal parameters because of the use of a lowpower, stabilized laser source as the probe. We also present the results of fluorescence measurements of the dye in the nanogold environment.

Influence of additives on the charactaristics of stone matrix asphalt

The increase in traffic growth and maintenance expenditures demands the urgent need for building better, long-lasting, and more efficient roads preventing or minimizing bituminous pavement distresses. Many of the principal distresses in pavements initiate or increase in severity due to the presence of water. In Kerala highways, where traditional dense graded mixtures are used for the surface courses, major distress is due to moisture induced damages. The Stone Matrix Asphalt (SMA) mixtures provide a durable surface course. Proven field performance of test track at Delhi recommends Stone Matrix Asphalt as a right choice to sustain severe climatic and heavy traffic conditions. But the concept of SMA in India is not so popularized and its application is very limited mainly due to the lack of proper specifications. This research is an attempt to study the influence of additives on the characteristics of SMA mixtures and to propose an ideal surface course for the pavements. The additives used for this investigation are coir, sisal, banana fibres (natural fibres), waste plastics (waste material) and polypropylene (polymer). A preliminary investigation is conducted to characterize the materials used in this study. Marshall test is conducted for optimizing the SMA mixtures (Control mixture-without additives and Stabilized mixtures with additives). Indirect tensile strength tests, compression strength tests, triaxial strength tests and drain down sensitivity tests are conducted to study the engineering properties of stabilized mixtures. The comparison of the performance of all stabilized mixtures with the control mixture and among themselves are carried out. A statistical analysis (SPSS package Ver.16) is performed to establish the findings of this study

Studies on L-glutamic acid Production using Brevibacterium sp.

The thesis comprises a set of experiments mainly focused on the improvement of L-glutamic acid fennentation. Much attention has been given to use of locally available raw materials, culturing the organism on inert solid substrates and also immobilization of the bacterial cells from the view point of long term utilization of biocatalyst and continuous operation of the stabilized system. Studies were also carried out for the down stream processing for the extraction and purification of L-glutamic acid. An attempt was made to study the morphological features of the microorganism including the cell premeability. In relation with the accumulation of glutamic acid within the cells an approach was made to study the behaviour of the Brevibacterium cells when they are exposed to hyper osmotic environment. Attempts were also made to study the requirement of iron and production of siderophores by this microbial strain. The search for a suitable nitrogen source for glutamate fermentation ended with a promising result that they got a potent urease activity and it can be utilized for many biotransfonnation studies. The entire thesis is presented in three sections, viz. introductory section, experimental section and the concluding section

Integrated Environment for Launch Vehicle Telemetry Data Management

The telemetry data processing operation intended for a given mission are pre-defined by an onboard telemetry configuration, mission trajectory and overall telemetry methodology have stabilized lately for ISRO vehicles. The given problem on telemetry data processing is reduced through hierarchical problem reduction whereby the sequencing of operations evolves as the control task and operations on data as the function task. The function task Input, Output and execution criteria are captured into tables which are examined by the control task and then schedules when the function task when the criteria is being met.

Waste plastic as a stabilizing additive in Stone Mastic Asphalt

The present study investigates the benefits of stabilizing the stone mastic asphalt (SMA) mixture in flexible pavement with shredded waste plastic. Conventional (without plastic) and the stabilized SMA mixtures were subjected to performance tests including Marshall Stability, tensile strength and compressive strength tests. Triaxial tests were also conducted with varying percentage bitumen by weight of mineral aggregate (6% to 8%) and by varying percentage plastic by weight of mix (6% to 12% with an increment of 1%). Plastic content of 10% by weight of bitumen is recommended for the improvement of the performance of Stone Mastic Asphalt mixtures. 10% plastic content gives an increase in the stability, split tensile strength and compressive strength of about 64%, 18% and 75% respectively compared to the conventional SMA mix. Triaxial test results show a 44% increase in cohesion and 3% decrease in angle of shearing resistance showing an increase in the shear strength. The drain down value decreases with an increase in plastic content and the value is only 0.09 % at 10% plastic content and proves to be an effective stabilizing additive in SMA mixtures

Influence Of Additives On The Drain Down Characteristics Of Stone Matrix Asphalt Mixtures

In Kerala highways, where traditional dense graded mixtures are used for the surface courses, major distress is due to moisture induced damages. Development of stabilized Stone Matrix Asphalt (SMA) mixtures for improved pavement performance has been the focus of research all over the world for the past few decades. Many successful attempts are made to stabilize SMA mixtures with synthetic fibres and polymers. India, being an agricultural economy produces fairly huge quantity of natural fibres such as coconut, sisal, banana, sugar cane, jute etc.. Now- a -days the disposal of waste plastics is a major concern for an eco- friendly sustainable environment. This paper focuses on the influence of additives like coir, sisal, banana fibres (natural fibres), waste plastics (waste material) and polypropylene (polymer) on the drain down characteristics of SMA mixtures. A preliminary investigation is conducted to characterize the materials used in this study. Drain down sensitivity tests are conducted to study the bleeding phenomena and drain down of SMA mixtures. Based on the drain down characteristics of the various stabilized mixtures it is inferred that the optimum fibre content is 0.3% by weight of mixture for all fibre mixtures irrespective of the type of fibre. For waste plastics and polypropylene stabilized SMA mixtures, the optimum additive contents are respectively 7% and 5% by weight of mixture. Due to the absorptive nature of fibres, fibre stabilizers are found to be more effective in reducing the drain down of the SMA mixture. The drain values for the waste plastics mix is within the required specification range. The coir fibre additive is the best among the fibres investigated. Sisal and banana fibre mixtures showed almost the same characteristics on stabilization.

N0-[(E)-Furan-2-ylmethylidene]pyridine- 3-carbohydrazide

The title compound, C11H9N3O2, exists in the E conformation with respect to the azomethane C N bond, and has the keto form. There are two independent molecules in the asymmetric unit and each of these features a slight slanting of the pyridine and furan rings, which form a dihedral angle of 14.96 (10) in one of the molecules and 5.53 (10) in the other. The crystal structure is stabilized by N—H O and N—H N hydrogen bonds, weak C—H O and C—H N hydrogen bonds and C—H interactions and – interactions [shortest centroid–centroid distance = 3.7864 (15) A ° ].

Szenarien zur zukünftigen Stromversorgung, kostenoptimierte Variationen zur Versorgung Europas und seiner Nachbarn mit Strom aus erneuerbaren Energien

Sowohl die Ressourcenproblematik als auch die drohenden Ausmaße der Klimaänderung lassen einen Umstieg auf andere Energiequellen langfristig unausweichlich erscheinen und mittelfristig als dringend geboten. Unabhängig von der Frage, auf welchem Niveau sich der Energiebedarf stabilisieren lässt, bleibt dabei zu klären, welche Möglichkeiten sich aus technischer und wirtschaftlicher Sicht in Zukunft zur Deckung unseres Energiebedarfs anbieten. Eine aussichtsreiche Option besteht in der Nutzung regenerativer Energien in ihrer ganzen Vielfalt. Die Arbeit "Szenarien zur zukünftigen Stromversorgung, kostenoptimierte Variationen zur Versorgung Europas und seiner Nachbarn mit Strom aus erneuerbaren Energien" konzentriert sich mit der Stromversorgung auf einen Teilaspekt der Energieversorgung, der zunehmend an Wichtigkeit gewinnt und als ein Schlüssel zur nachhaltigen Energieversorgung interpretiert werden kann. Die Stromversorgung ist heute weltweit für etwa die Hälfte des anthropogenen CO2-Ausstoßes verantwortlich. In dieser Arbeit wurden anhand verschiedener Szenarien Möglichkeiten einer weitgehend CO2–neutralen Stromversorgung für Europa und seine nähere Umgebung untersucht, wobei das Szenariogebiet etwa 1,1 Mrd. Einwohner und einen Stromverbrauch von knapp 4000 TWh/a umfasst. Dabei wurde untersucht, wie die Stromversorgung aufgebaut sein sollte, damit sie möglichst kostengünstig verwirklicht werden kann. Diese Frage wurde beispielsweise für Szenarien untersucht, in denen ausschließlich heute marktverfügbare Techniken berücksichtigt wurden. Auch der Einfluss der Nutzung einiger neuer Technologien, die bisher noch in Entwicklung sind, auf die optimale Gestaltung der Stromversorgung, wurde anhand einiger Beispiele untersucht. Die Konzeption der zukünftigen Stromversorgung sollte dabei nach Möglichkeit objektiven Kriterien gehorchen, die auch die Vergleichbarkeit verschiedener Versorgungsansätze gewährleisten. Dafür wurde ein Optimierungsansatz gewählt, mit dessen Hilfe sowohl bei der Konfiguration als auch beim rechnerischen Betrieb des Stromversorgungssystems weitgehend auf subjektive Entscheidungsprozesse verzichtet werden kann. Die Optimierung hatte zum Ziel, für die definierte möglichst realitätsnahe Versorgungsaufgabe den idealen Kraftwerks- und Leitungspark zu bestimmen, der eine kostenoptimale Stromversorgung gewährleistet. Als Erzeugungsoptionen werden dabei u.a. die Nutzung Regenerativer Energien durch Wasserkraftwerke, Windenergiekonverter, Fallwindkraftwerke, Biomassekraftwerke sowie solare und geothermische Kraftwerke berücksichtigt. Abhängig von den gewählten Randbedingungen ergaben sich dabei unterschiedliche Szenarien. Das Ziel der Arbeit war, mit Hilfe unterschiedlicher Szenarien eine breite Basis als Entscheidungsgrundlage für zukünftige politische Weichenstellungen zu schaffen. Die Szenarien zeigen Optionen für eine zukünftige Gestaltung der Stromversorgung auf, machen Auswirkungen verschiedener – auch politischer – Rahmenbedingungen deutlich und stellen so die geforderte Entscheidungsgrundlage bereit. Als Grundlage für die Erstellung der Szenarien mussten die verschiedenen Potentiale erneuerbarer Energien in hoher zeitlicher und räumlicher Auflösung ermittelt werden, mit denen es erstmals möglich war, die Fragen einer großräumigen regenerativen Stromversorgung ohne ungesicherte Annahmen anhand einer verlässlichen Datengrundlage anzugehen. Auch die Charakteristika der verschiedensten Energiewandlungs- und Transportsysteme mussten studiert werden und sind wie deren Kosten und die verschiedenen Potentiale in der vorliegenden Arbeit ausführlich diskutiert. Als Ausgangsszenario und Bezugspunkt dient ein konservatives Grundszenario. Hierbei handelt es sich um ein Szenario für eine Stromversorgung unter ausschließlicher Nutzung erneuerbarer Energien, die wiederum ausschließlich auf heute bereits entwickelte Technologien zurückgreift und dabei für alle Komponenten die heutigen Kosten zugrundelegt. Dieses Grundszenario ist dementsprechend auch als eine Art konservative Worst-Case-Abschätzung für unsere Zukunftsoptionen bei der regenerativen Stromversorgung zu verstehen. Als Ergebnis der Optimierung basiert die Stromversorgung beim Grundszenario zum größten Teil auf der Stromproduktion aus Windkraft. Biomasse und schon heute bestehende Wasserkraft übernehmen den überwiegenden Teil der Backup-Aufgaben innerhalb des – mit leistungsstarker HGÜ (Hochspannungs–Gleichstrom–Übertragung) verknüpften – Stromversorgungsgebiets. Die Stromgestehungskosten liegen mit 4,65 €ct / kWh sehr nahe am heute Üblichen. Sie liegen niedriger als die heutigen Preisen an der Strombörse. In allen Szenarien – außer relativ teuren, restriktiv ”dezentralen” unter Ausschluss großräumig länderübergreifenden Stromtransports – spielt der Stromtransport eine wichtige Rolle. Er wird genutzt, um Ausgleichseffekte bei der dargebotsabhängigen Stromproduktion aus erneuerbaren Quellen zu realisieren, gute kostengünstige Potentiale nutzbar zu machen und um die Speicherwasserkraft sowie die dezentral genutzte Biomasse mit ihrer Speicherfähigkeit für großräumige Backup-Aufgaben zu erschließen. Damit erweist sich der Stromtransport als einer der Schlüssel zu einer kostengünstigen Stromversorgung. Dies wiederum kann als Handlungsempfehlung bei politischen Weichenstellungen interpretiert werden, die demnach gezielt auf internationale Kooperation im Bereich der Nutzung erneuerbarer Energien setzen und insbesondere den großräumigen Stromtransport mit einbeziehen sollten. Die Szenarien stellen detaillierte und verlässliche Grundlagen für wichtige politische und technologische Zukunftsentscheidungen zur Verfügung. Sie zeigen, dass bei internationaler Kooperation selbst bei konservativen Annahmen eine rein regenerative Stromversorgung möglich ist, die wirtschaftlich ohne Probleme zu realisieren wäre und verweisen den Handlungsbedarf in den Bereich der Politik. Eine wesentliche Aufgabe der Politik läge darin, die internationale Kooperation zu organisieren und Instrumente für eine Umgestaltung der Stromversorgung zu entwickeln. Dabei kann davon ausgegangen werden, dass nicht nur ein sinnvoller Weg zu einer CO2–neutralen Stromversorgung beschritten würde, sondern sich darüber hinaus ausgezeichnete Entwicklungsperspektiven für die ärmeren Nachbarstaaten der EU und Europas eröffnen.

The Navier-Stokes Equations with Time Delay

In the present paper we use a time delay epsilon > 0 for an energy conserving approximation of the nonlinear term of the non-stationary Navier-Stokes equations. We prove that the corresponding initial value problem (N_epsilon)in smoothly bounded domains G \subseteq R^3 is well-posed. Passing to the limit epsilon \rightarrow 0 we show that the sequence of stabilized solutions has an accumulation point such that it solves the Navier-Stokes problem (N_0) in a weak sense (Hopf).

Effects of tillage on processes of organic matter sequestration

To increase the organic matter (OM) content in the soil is one main goal in arable soil management. The adoption of tillage systems with reduced tillage depth and/or frequency (reduced tillage) or of no-tillage was found to increase the concentration of soil OM compared to conventional tillage (CT; ploughing to 20-30 cm). However, the underlying processes are not yet clear and are discussed contradictorily. So far, few investigations were conducted on tillage systems with a shallow tillage depth (minimum tillage = MT; maximum tillage depth of 10 cm). A better understanding of the interactions between MT implementation and changes in OM transformation in soils is essential in order to evaluate the possible contribution of MT to a sustainable management of arable soils. The objectives of the present thesis were (i) to compare OM concentrations, microbial biomass, water-stable aggregates, and particulate OM (POM) between CT and MT soils, (ii) to estimate the temporal variability of water-stable aggregate size classes occurring in the field and the dynamics of macroaggregate (>250 µm) formation and disruption under controlled conditions, (iii) to investigate whether a lower disruption or a higher formation rate accounts for a higher occurrence of macroaggregates under MT compared to CT, (iv) to determine which fraction is the major agent for storing the surplus of OM found under MT compared to CT, and (v) to observe the early OM transformation after residue incorporation in different tillage systems simulated. Two experimental sites (Garte-Süd and Hohes Feld) near Göttingen, Germany, were investigated. Soil type of both sites was a Haplic Luvisol. Since about 40 years, both sites receive MT by a rotary harrow (to 5-8 cm depth) and CT by a plough (to 25 cm depth). Surface soils (0-5 cm) and subsoils (10-20 cm) of two sampling dates (after fallow and directly after tillage) were investigated for concentrations of organic C (Corg) and total N (N), different water-stable aggregate size classes, different density fractions (for the sampling date after fallow only), microbial biomass, and for biochemically stabilized Corg and N (by acid hydrolysis; for the sampling date after tillage only). In addition, two laboratory incubations were performed under controlled conditions: Firstly, MT and CT soils were incubated (28 days at 22°C) as bulk soil and with destroyed macroaggregates in order to estimate the importance of macroaggregates for the physical protection of the very labile OM against mineralization. Secondly, in a microcosm experiment simulating MT and CT systems with soil <250 µm and with 15N and 13C labelled maize straw incorporated to different depths, the mineralization, the formation of new macroaggregates, and the partitioning of the recently added C and N were followed (28 days at 15°C). Forty years of MT regime led to higher concentrations of microbial biomass and of Corg and N compared to CT, especially in the surface soil. After fallow and directly after tillage, a higher proportion of water-stable macroaggregates rich in OM was found in the MT (36% and 66%, respectively) than in the CT (19% and 47%, respectively) surface soils of both sites (data shown are of the site Garte-Süd only). The subsoils followed the same trend. For the sampling date after fallow, no differences in the POM fractions were found but there was more OM associated to the mineral fraction detected in the MT soils. A large temporal variability was observed for the abundance of macroaggregates. In the field and in the microcosm simulations, macroaggregates were found to have a higher formation rate after the incorporation of residues under MT than under CT. Thus, the lower occurrence of macroaggregates in CT soils cannot be attributed to a higher disruption but to a lower formation rate. A higher rate of macroaggregate formation in MT soils may be due to (i) the higher concentrated input of residues in the surface soil and/or (ii) a higher abundance of fungal biomass in contrast to CT soils. Overall, as a location of storage of the surplus of OM detected under MT compared to CT, water-stable macroaggregates were found to play a key role. In the incubation experiment, macroaggregates were not found to protect the very labile OM against mineralization. Anyway, the surplus of OM detected after tillage in the MT soil was biochemically degradable. MT simulations in the microcosm experiment showed a lower specific respiration and a less efficient translocation of recently added residues than the CT simulations. Differences in the early processes of OM translocation between CT and MT simulations were attributed to a higher residue to soil ratio and to a higher proportion of fungal biomass in the MT simulations. Overall, MT was found to have several beneficial effects on the soil structure and on the storage of OM, especially in the surface soil. Furthermore, it was concluded that the high concentration of residues in the surface soil of MT may alter the processes of storage and decomposition of OM. In further investigations, especially analysis of the residue-soil-interface and of effects of the depth of residue incorporation should be emphasised. Moreover, further evidence is needed on differences in the microbial community between CT and MT soils.

Application of biogas slurries from energy crops to arable soils and their impact on carbon and nitrogen dynamics

The use of renewable primary products as co-substrate or single substrate for biogas production has increased consistently over the last few years. Maize silage is the preferential energy crop used for fermentation due to its high methane (CH4) yield per hectare. Equally, the by-product, namely biogas slurry (BS), is used with increasing frequency as organic fertilizer to return nutrients to the soil and to maintain or increase the organic matter stocks and soil fertility. Studies concerning the application of energy crop-derived BS on the carbon (C) and nitrogen (N) mineralization dynamics are scarce. Thus, this thesis focused on the following objectives: I) The determination of the effects caused by rainfall patterns on the C and N dynamics from two contrasting organic fertilizers, namely BS from maize silage and composted cattle manure (CM), by monitoring emissions of nitrous oxide (N2O), carbon dioxide (CO2) and CH4 as well as leaching losses of C and N. II) The investigation of the impact of differences in soil moisture content after the application of BS and temperature on gaseous emissions (CO2, N2O and CH4) and leaching of C and N compounds. III) A comparison of BS properties obtained from biogas plants with different substrate inputs and operating parameters and their effect on C and N dynamics after application to differently textured soils with varying application rates and water contents. For the objectives I) and II) two experiments (experiment I and II) using undisturbed soil cores of a Haplic Luvisol were carried out. Objective III) was studied on a third experiment (experiment III) with disturbed soil samples. During experiment I three rainfall patterns were implemented including constant irrigation, continuous irrigation with periodic heavy rainfall events, and partial drying with rewetting periods. Biogas slurry and CM were applied at a rate of 100 kg N ha-1. During experiment II constant irrigation and an irrigation pattern with partial drying with rewetting periods were carried out at 13.5°C and 23.5°C. The application of BS took place either directly before a rewetting period or one week after the rewetting period stopped. Experiment III included two soils of different texture which were mixed with ten BS’s originating from ten different biogas plants. Treatments included low, medium and high BS-N application rates and water contents ranging from 50% to 100% of water holding capacity (WHC). Experiment I and II showed that after the application of BS cumulative N2O emissions were 4 times (162 mg N2O-N m-2) higher compared to the application of CM caused by a higher content of mineral N (Nmin) in the form of ammonium (NH4+) in the BS. The cumulative emissions of CO2, however, were on the same level for both fertilizers indicating similar amounts of readily available C after composting and fermentation of organic material. Leaching losses occurred predominantly in the mineral form of nitrate (NO3-) and were higher in BS amended soils (9 mg NO3--N m-2) compared to CM amended soils (5 mg NO3--N m-2). The rainfall pattern in experiment I and II merely affected the temporal production of C and N emissions resulting in reduced CO2 and enhanced N2O emissions during stronger irrigation events, but showed no effect on the cumulative emissions. Overall, a significant increase of CH4 consumption under inconstant irrigation was found. The time of fertilization had no effect on the overall C and N dynamics. Increasing temperature from 13.5°C to 23.5°C enhanced the CO2 and N2O emissions by a factor of 1.7 and 3.7, respectively. Due to the increased microbial activity with increasing temperature soil respiration was enhanced. This led to decreasing oxygen (O2) contents which in turn promoted denitrification in soil due to the extension of anaerobic microsites. Leaching losses of NO3- were also significantly affected by increasing temperature whereas the consumption of CH4 was not affected. The third experiment showed that the input materials of biogas plants affected the properties of the resulting BS. In particular the contents of DM and NH4+ were determined by the amount of added plant biomass and excrement-based biomass, respectively. Correlations between BS properties and CO2 or N2O emissions were not detected. Solely the ammonia (NH3) emissions showed a positive correlation with NH4+ content in BS as well as a negative correlation with the total C (Ct) content. The BS-N application rates affected the relative CO2 emissions (% of C supplied with BS) when applied to silty soil as well as the relative N2O emissions (% of N supplied with BS) when applied to sandy soil. The impacts on the C and N dynamics induced by BS application were exceeded by the differences induced by soil texture. Presumably, due to the higher clay content in silty soils, organic matter was stabilized by organo-mineral interactions and NH4+ was adsorbed at the cation exchange sites. Different water contents induced highest CO2 emissions and therefore optimal conditions for microbial activity at 75% of WHC in both soils. Cumulative nitrification was also highest at 75% and 50% of WHC whereas the relative N2O emissions increased with water content and showed higher N2O losses in sandy soils. In summary it can be stated that the findings of the present thesis confirmed the high fertilizer value of BS’s, caused by high concentrations of NH4+ and labile organic compounds such as readily available carbon. These attributes of BS’s are to a great extent independent of the input materials of biogas plants. However, considerably gaseous and leaching losses of N may occur especially at high moisture contents. The emissions of N2O after field application corresponded with those of animal slurries.

Unsymmetrisch substituierte N-heterocyclische Carbene mit einem 1,1 ʹ-Ferrocendiyl-Rückgrat und N-heterocyclische Carbene als Adsorbatspezies für selbstorganisierende Monolagen

Aufbauend auf den Arbeiten von Bielawski et al. und Siemeling et al. wurden im Rahmen dieser Arbeit unsymmetrisch substituierte N-heterocyclische Carbene mit einem 1,1ʹ-Ferrocendiyl-Rückgrat synthetisiert. Ausgehend von der literaturbekannten Verbindung 1,1’-Diaminoferrocen gelang die Einführung der exocyclischen Substituenten an den Stickstoffatomen lediglich durch die Anpassung der Stöchiometrie in den einzelnen Syntheseschritten. Es wurden die folgenden drei NHCs synthetisiert: N-(2-Adamantyl)-N’-neopentyldiaminocarben[3]ferrocenophan (Ad/Np), N-Neopentyl-N’-phenyldiaminocarben[3]ferrocenophan (Ph/Np) und N-(9-Anthracenylmethyl)-N’-neopentyldiaminocarben[3]ferrocenophan (Acm/Np). Das Carben Ad/Np konnte dabei erfolgreich isoliert werden, während die anderen zwei Carbene als Liganden in Komplexen des Typs [RhCl(COD)(NHC)] stabilisiert wurden. Von allen drei Carbenen wurden Rhodium-Carben-Komplexe des Typs [RhCl(COD)(NHC)] und cis-[RhCl(CO)2(NHC)] synthetisiert. Anhand der röntgenkristallographischen und NMR-spektroskopischen Untersuchungen dieser Rhodiumkomplexe konnten in allen sechs Komplexen anagostische Wechselwirkungen zwischen dem zentralen Rhodiumatom und den Wasserstoffatomen der exocyclischen Substituenten, die sich in α-Position zu den Stickstoffatomen befinden, nachgewiesen werden. Des Weiteren wurden anhand der cis-[RhCl(CO)2(NHC)]-Komplexe die TEP-Werte der Carbene bestimmt. Gemessen in DCM betragen diese 2049 cm-1 (Ad/Np), 2049 cm-1 (Ph/Np) und 2051 cm-1 (Acm/Np). Unabhängig von den unsymmetrisch substituierten NHCs mit einem 1,1ʹ-Ferrocendiyl-Rückgrat wurde im Rahmen dieser Arbeit die Eignung von NHCs als Adsorbatspezies für selbstorganisierende Monolagen überprüft. Hierzu wurden Tetraalkylimidazol-2-ylidene synthetisiert, welche als 0.01 mM Lösung auf Gold(111)-Substrate aufgebracht wurden. Die Goldsubstrate wurden anschließend mittels XPS untersucht. Die XPS-Analyse der modifizierten Goldsubstrate zeigte, dass eine Bindung der Carbene auf der Oberfläche stattgefunden hat. Es zeigte sich allerdings auch, dass keine SAM gebildet wurden, da die Oberfläche signifikant mit kohlen- und sauerstoffbasierten Verbindungen kontaminiert ist. Dabei kann vermutet werden, dass die Carbene nicht ausschließlich auf der Goldoberfläche selbst, sondern auch mit den auf der Oberfläche befindlichen Verbindungen reagiert haben.