Preparation and applications of periodical gold nanoparticle arrays

Diese Arbeit beschäftigt sich mit der Herstellung und Anwendungen von periodischen Goldnanopartikel-Arrays (PPAs), die mit Hilfe von Nanosphären-Lithografie hergestellt wurden. In Abhängigkeit der verwendeten Nanosphären-Größe wurden dabei entweder kleine dreieckige Nanopartikel (NP) (bei Verwendung von Nanosphären mit einem Durchmesser von 330 nm) oder große dreieckige NPD sowie leicht gestreckte NP (bei Verwendung von Nanosphären mit einem Durchmesser von 1390 nm) hergestellt. Die Charakterisierung der PPAs erfolgte mit Hilfe von Rasterkraftmikroskopie, Rasterelektronenmikroskopie und optischer Spektroskopie. Die kleinen NP besitzen ein Achsverhältnis (AV) von 2,47 (Kantenlänge des NPs: (74+/-6) nm, Höhe: (30+/-4) nm. Die großen dreieckigen NP haben ein AV von 3 (Kantenlänge des NPs:(465+/-27) nm, Höhe: (1530+/-10) nm) und die leicht gestreckten NP (die aufgrund der Ausbildung von Doppelschichten ebenfalls auf der gleichen Probe erzeugt wurden) haben eine Länge von (364+/-16)nm, eine Breite von (150+/-20) nm und eine Höhe von (150+/-10)nm. Die optischen Eigenschaften dieser NP werden durch lokalisierte Oberflächenplasmon-Polariton Resonanzen (LPPRs) dominiert, d.h. von einem eingestrahlten elektromagnetischen Feld angeregte kollektive Schwingungen der Leitungsbandelektronen. In dieser Arbeit wurden drei signifikante Herausforderungen für Plasmonik-Anwendungen bearbeitet, welche die einzigartigen optischen Eigenschaften dieser NP ausnutzen. Erstens wurden Ergebnisse der selektiven und präzisen Größenmanipulation und damit einer Kontrolle der interpartikulären Abstände von den dreieckigen Goldnanopartikel mit Hilfe von ns-gepulstem Laserlicht präsentiert. Die verwendete Methode basiert hierbei auf der Größen- und Formabhängigkeit der LPPRs der NP. Zweitens wurde die sensorischen Fähigkeiten von Gold-NP ausgenutzt, um die Bildung von molekularen Drähten auf den PPAs durch schrittweise Zugabe von unterschiedlichen molekularen Spezies zu untersuchen. Hierbei wurde die Verschiebung der LSPPR in den optischen Spektren dazu ausgenutzt, die Bildung der Nanodrähte zu überwachen. Drittens wurden Experimente vorgestellt, die sich die lokale Feldverstärkung von NP zu nutze machen, um eine hochgeordnete Nanostrukturierung von Oberflächen mittels fs-gepulstem Laserlicht zu bewerkstelligen. Dabei zeigt sich, dass neben der verwendeten Fluenz die Polarisationsrichtung des eingestrahlten Laserlichts in Bezug zu der NP-Orientierung sowie die Größe der NP äußerst wichtige Parameter für die Nanostrukturierung darstellen. So konnten z.B. Nanolöcher erzeugt werden, die bei höheren Fluenzen zu Nanogräben und Nanokanälen zusammen wuchsen. Zusammengefasst lässt sich sagen, dass die in dieser Arbeit gewonnen Ergebnisse von enormer Wichtigkeit für weitere Anwendungen sind.

Determination of yield and quality parameters of energy crops applying laboratory and field spectroscopy

A real-time analysis of renewable energy sources, such as arable crops, is of great importance with regard to an optimised process management, since aspects of ecology and biodiversity are considered in crop production in order to provide a sustainable energy supply by biomass. This study was undertaken to explore the potential of spectroscopic measurement procedures for the prediction of potassium (K), chloride (Cl), and phosphate (P), of dry matter (DM) yield, metabolisable energy (ME), ash and crude fibre contents (ash, CF), crude lipid (EE), nitrate free extracts (NfE) as well as of crude protein (CP) and nitrogen (N), respectively in pretreated samples and undisturbed crops. Three experiments were conducted, one in a laboratory using near infrared reflectance spectroscopy (NIRS) and two field spectroscopic experiments. Laboratory NIRS measurements were conducted to evaluate to what extent a prediction of quality parameters is possible examining press cakes characterised by a wide heterogeneity of their parent material. 210 samples were analysed subsequent to a mechanical dehydration using a screw press. Press cakes serve as solid fuel for thermal conversion. Field spectroscopic measurements were carried out with regard to further technical development using different field grown crops. A one year lasting experiment over a binary mixture of grass and red clover examined the impact of different degrees of sky cover on prediction accuracies of distinct plant parameters. Furthermore, an artificial light source was used in order to evaluate to what extent such a light source is able to minimise cloud effects on prediction accuracies. A three years lasting experiment with maize was conducted in order to evaluate the potential of off-nadir measurements inside a canopy to predict different quality parameters in total biomass and DM yield using one sensor for a potential on-the-go application. This approach implements a measurement of the plants in 50 cm segments, since a sensor adjusted sideways is not able to record the entire plant height. Calibration results obtained by nadir top-of-canopy reflectance measurements were compared to calibration results obtained by off-nadir measurements. Results of all experiments approve the applicability of spectroscopic measurements for the prediction of distinct biophysical and biochemical parameters in the laboratory and under field conditions, respectively. The estimation of parameters could be conducted to a great extent with high accuracy. An enhanced basis of calibration for the laboratory study and the first field experiment (grass/clover-mixture) yields in improved robustness of calibration models and allows for an extended application of spectroscopic measurement techniques, even under varying conditions. Furthermore, off-nadir measurements inside a canopy yield in higher prediction accuracies, particularly for crops characterised by distinct height increment as observed for maize.

Modelling and simulation of a photovoltaic fuel cell hybrid system

A stand-alone power system is an autonomous system that supplies electricity to the user load without being connected to the electric grid. This kind of decentralized system is frequently located in remote and inaccessible areas. It is essential for about one third of the world population which are living in developed or isolated regions and have no access to an electricity utility grid. The most people live in remote and rural areas, with low population density, lacking even the basic infrastructure. The utility grid extension to these locations is not a cost effective option and sometimes technically not feasible. The purpose of this thesis is the modelling and simulation of a stand-alone hybrid power system, referred to as “hydrogen Photovoltaic-Fuel Cell (PVFC) hybrid system”. It couples a photovoltaic generator (PV), an alkaline water electrolyser, a storage gas tank, a proton exchange membrane fuel cell (PEMFC), and power conditioning units (PCU) to give different system topologies. The system is intended to be an environmentally friendly solution since it tries maximising the use of a renewable energy source. Electricity is produced by a PV generator to meet the requirements of a user load. Whenever there is enough solar radiation, the user load can be powered totally by the PV electricity. During periods of low solar radiation, auxiliary electricity is required. An alkaline high pressure water electrolyser is powered by the excess energy from the PV generator to produce hydrogen and oxygen at a pressure of maximum 30bar. Gases are stored without compression for short- (hourly or daily) and long- (seasonal) term. A proton exchange membrane (PEM) fuel cell is used to keep the system’s reliability at the same level as for the conventional system while decreasing the environmental impact of the whole system. The PEM fuel cell consumes gases which are produced by an electrolyser to meet the user load demand when the PV generator energy is deficient, so that it works as an auxiliary generator. Power conditioning units are appropriate for the conversion and dispatch the energy between the components of the system. No batteries are used in this system since they represent the weakest when used in PV systems due to their need for sophisticated control and their short lifetime. The model library, ISET Alternative Power Library (ISET-APL), is designed by the Institute of Solar Energy supply Technology (ISET) and used for the simulation of the hybrid system. The physical, analytical and/or empirical equations of each component are programmed and implemented separately in this library for the simulation software program Simplorer by C++ language. The model parameters are derived from manufacturer’s performance data sheets or measurements obtained from literature. The identification and validation of the major hydrogen PVFC hybrid system component models are evaluated according to the measured data of the components, from the manufacturer’s data sheet or from actual system operation. Then, the overall system is simulated, at intervals of one hour each, by using solar radiation as the primary energy input and hydrogen as energy storage for one year operation. A comparison between different topologies, such as DC or AC coupled systems, is carried out on the basis of energy point of view at two locations with different geographical latitudes, in Kassel/Germany (Europe) and in Cairo/Egypt (North Africa). The main conclusion in this work is that the simulation method of the system study under different conditions could successfully be used to give good visualization and comparison between those topologies for the overall performance of the system. The operational performance of the system is not only depending on component efficiency but also on system design and consumption behaviour. The worst case of this system is the low efficiency of the storage subsystem made of the electrolyser, the gas storage tank, and the fuel cell as it is around 25-34% at Cairo and 29-37% at Kassel. Therefore, the research for this system should be concentrated in the subsystem components development especially the fuel cell.

Status and Potential of Smallholder Livestock Production Systems in Xishuangbanna, southern P.R. China

With Chinas rapid economic development during the last decades, the national demand for livestock products has quadrupled within the last 20 years. Most of that increase in demand has been answered by subsidized industrialized production systems, while million of smallholders, which still provide the larger share of livestock products in the country, have been neglected. Fostering those systems would help China to lower its strong urban migration streams, enhance the livelihood of poorer rural population and provide environmentally save livestock products which have a good chance to satisfy customers demand for ecological food. Despite their importance, China’s smallholder livestock keepers have not yet gained appropriate attention from governmental authorities and researchers. However, profound analysis of those systems is required so that adequate support can lead to a better resource utilization and productivity in the sector. To this aim, this pilot study analyzes smallholder livestock production systems in Xishuangbanna, located in southern China. The area is bordered by Lao and Myanmar and geographically counts as tropical region. Its climate is characterized by dry and temperate winters and hot summers with monsoon rains from May to October. While the regionis plain, at about 500 m asl above sea level in the south, outliers of the Himalaya mountains reach out into the north of Xishuangbanna, where the highest peak reaches 2400 m asl. Except of one larger city, Jinghong, Xishuangbanna mainly is covered by tropical rainforest, areas under agricultural cultivation and villages. The major income is generated through inner-Chinese tourism and agricultural production. Intensive rubber plantations are distinctive for the lowland plains while small-scaled traditional farms are scattered in the mountane regions. In order to determine the current state and possible future chances of smallholder livestock production in that region, this study analyzed the current status of the smallholder livestock sector in the Naban River National Nature Reserve (NRNNR), an area which is largely representative for the whole prefecture. It covers an area of about 50square kilometer and reaches from 470 up to 2400 m asl. About 5500 habitants of different ethnic origin are situated in 24 villages. All data have been collected between October 2007 and May 2010. Three major objectives have been addressed in the study: 1. Classifying existing pig production systems and exploring respective pathways for development 2. Quantifying the performance of pig breeding systemsto identify bottlenecks for production 3. Analyzing past and current buffalo utilization to determine the chances and opportunities of buffalo keeping in the future In order to classify the different pig production s ystems, a baseline survey (n=204, stratified cluster sampling) was carried out to gain data about livestock species, numbers, management practices, cultivated plant species and field sizes as well associo-economic characteristics. Sampling included two clusters at village level (altitude, ethnic affiliation), resulting in 13 clusters of which 13-17 farms were interviewed respectively. Categorical Principal Component Analysis (CatPCA) and a two-step clustering algorithm have been applied to identify determining farm characteristics and assort recorded households into classes of livestock production types. The variables keep_sow_yes/no, TLU_pig, TLU_buffalo, size_of_corn_fields, altitude_class, size_of_tea_plantationand size_of_rubber_fieldhave been found to be major determinants for the characterization of the recorded farms. All farms have extensive or semi-intensive livestock production, pigs and buffaloes are predominant livestock species while chicken and aquaculture are available but play subordinate roles for livelihoods. All pig raisers rely on a single local breed, which is known as Small Ear Pig (SMEP) in the region. Three major production systemshave been identified: Livestock-corn based LB; 41%), rubber based (RB; 39%) and pig based (PB;20%) systems. RB farms earn high income from rubber and fatten 1.9 ±1.80 pigs per household (HH), often using purchased pig feed at markets. PB farms own similar sized rubber plantations and raise 4.7 ±2.77 pigs per HH, with fodder mainly being cultivated and collected in theforest. LB farms grow corn, rice and tea and keep 4.6 ±3.32 pigs per HH, also fed with collected and cultivated fodder. Only 29% of all pigs were marketed (LB: 20%; RB: 42%; PB: 25%), average annual mortality was 4.0 ±4.52 pigs per farm (LB: 4.6 ±3.68; RB: 1.9 ±2.14; PB: 7.1 ±10.82). Pig feed mainly consists of banana pseudo stem, corn and rice hives and is prepared in batches about two to three times per week. Such fodder might be sufficient in energy content but lacks appropriate content of protein. Pigs therefore suffer from malnutrition, which becomes most critical in the time before harvest season around October. Farmers reported high occurrences of gastrointestinal parasites in carcasses and often pig stables were wet and filled with manure. Deficits in nutritional and hygienic management are major limits for development and should be the first issues addressed to improve productivity. SME pork was found to be known and referred by local customers in town and by richer lowland farmers. However, high prices and lacking availability of SME pork at local wet-markets were the reasons which limited purchase. If major management constraints are overcome, pig breeders (PB and LB farms) could increase the share of marketed pigs for town markets and provide fatteners to richer RB farmers. RB farmers are interested in fattening pigs for home consumption but do not show any motivation for commercial pig raising. To determine the productivity of input factors in pig production, eproductive performance, feed quality and quantity as well as weight development of pigs under current management were recorded. The data collection included a progeny history survey covering 184 sows and 437 farrows, bi-weekly weighing of 114 pigs during a 16-months time-span on 21 farms (10 LB and 11 PB) as well as the daily recording of feed quality and quantity given to a defined number of pigs on the same 21 farms. Feed samples of all recorded ingredients were analyzed for their respective nutrient content. Since no literature values on thedigestibility of banana pseudo stem – which is a major ingredient of traditional pig feed in NRNNR – were found, a cross-sectional digestibility trial with 2x4 pigs has been conducted on a station in the research area. With the aid of PRY Herd Life Model, all data have been utilized to determine thesystems’ current (Status Quo = SQ) output and the productivity of the input factor “feed” in terms of saleable life weight per kg DM feed intake and monetary value of output per kg DM feed intake.Two improvement scenarios were simulated, assuming 1) that farmers adopt a culling managementthat generates the highest output per unit input (Scenario 1; SC I) and 2) that through improved feeding, selected parameters of reproduction are improved by 30% (SC II). Daily weight gain averaged 55 ± 56 g per day between day 200 and 600. The average feed energy content of traditional feed mix was 14.92 MJ ME. Age at first farrowing averaged 14.5 ± 4.34 months, subsequent inter-farrowing interval was 11.4 ± 2.73 months. Littersize was 5.8 piglets and weaning age was 4.3 ± 0.99 months. 18% of piglets died before weaning. Simulating pig production at actualstatus, it has been show that monetary returns on inputs (ROI) is negative (1:0.67), but improved (1:1.2) when culling management was optimized so that highest output is gained per unit feed input. If in addition better feeding, controlled mating and better resale prices at fixed dates were simulated, ROI further increased to 1:2.45, 1:2.69, 1:2.7 and 1:3.15 for four respective grower groups. Those findings show the potential of pork production, if basic measures of improvement are applied. Futureexploration of the environment, including climate, market-season and culture is required before implementing the recommended measures to ensure a sustainable development of a more effective and resource conserving pork production in the future. The two studies have shown that the production of local SME pigs plays an important role in traditional farms in NRNNR but basic constraints are limiting their productivity. However, relatively easy approaches are sufficient for reaching a notable improvement. Also there is a demand for more SME pork on local markets and, if basic constraints have been overcome, pig farmers could turn into more commercial producers and provide pork to local markets. By that, environmentally safe meat can be offered to sensitive consumers while farmers increase their income and lower the risk of external shocks through a more diverse income generating strategy. Buffaloes have been found to be the second important livestock species on NRNNR farms. While they have been a core resource of mixed smallholderfarms in the past, the expansion of rubber tree plantations and agricultural mechanization are reasons for decreased swamp buffalo numbers today. The third study seeks to predict future utilization of buffaloes on different farm types in NRNNR by analyzing the dynamics of its buffalo population and land use changes over time and calculating labor which is required for keeping buffaloes in view of the traction power which can be utilized for field preparation. The use of buffaloes for field work and the recent development of the egional buffalo population were analyzed through interviews with 184 farmers in 2007/2008 and discussions with 62 buffalo keepers in 2009. While pig based farms (PB; n=37) have abandoned buffalo keeping, 11% of the rubber based farms (RB; n=71) and 100% of the livestock-corn based farms (LB; n=76) kept buffaloes in 2008. Herd size was 2.5 ±1.80 (n=84) buffaloes in early 2008 and 2.2 ±1.69 (n=62) in 2009. Field work on own land was the main reason forkeeping buffaloes (87.3%), but lending work buffaloes to neighbors (79.0%) was also important. Other purposes were transport of goods (16.1%), buffalo trade (11.3%) and meat consumption(6.4%). Buffalo care required 6.2 ±3.00 working hours daily, while annual working time of abuffalo was 294 ±216.6 hours. The area ploughed with buffaloes remained constant during the past 10 years despite an expansion of land cropped per farm. Further rapid replacement of buffaloes by tractors is expected in the near future. While the work economy is drastically improved by the use of tractors, buffaloes still can provide cheap work force and serve as buffer for economic shocks on poorer farms. Especially poor farms, which lack alternative assets that could quickly be liquidizedin times of urgent need for cash, should not abandon buffalo keeping. Livestock has been found to be a major part of small mixed farms in NRNNR. The general productivity was low in both analyzed species, buffaloes and pigs. Productivity of pigs can be improved through basic adjustments in feeding, reproductive and hygienic management, and with external support pig production could further be commercialized to provide pork and weaners to local markets and fattening farms. Buffalo production is relatively time intensive, and only will be of importance in the future to very poor farms and such farms that cultivate very small terraces on steep slopes. These should be encouraged to further keep buffaloes. With such measures, livestock production in NRNNR has good chances to stay competitive in the future.

Varying the dietary supply of C and N to manipulate the manure composition of water buffalo heifers in Oman

Optimizing the composition of manure has the potential to reduce nutrient losses to the environment and to increase crop yields. In this study the effect of dietary ratios of carbon (C) to nitrogen (N) and neutral detergent fibre (NDF) to soluble carbohydrates (SC) on faeces composition of water buffalo heifers was assessed. Two digestibility trials were conducted with 12 animals each, fed one control and four test diets composed to achieve (1) high C/N and high NDF/SC ratios (HH), (2) low C/N and low NDF/SC ratios (LL), (3) high C/N and low NDF/SC ratios (HL) and (4) low C/N and high NDF/SC (LH) ratios. Faecal C/N ratios were generally lower than dietary C/N ratios, but the reduction was especially large for high C/N ratio diets (HH=55 %, HL=51 %). Faecal N concentration was positively correlated (r^2 = 0.6; P < 0.001) with N intake, but the increase in faecal N was more pronounced for diets that supplied low amounts of N. Faecal NDF concentration was positively related to NDF intake (r^2 = 0.42; P < 0.001), as well as the faecal C/N ratio (r^2 = 0.3; P < 0.001). Results demonstrate that C/N ratio and NDF concentration of buffalo manure were affected by diet composition. Diets with high C/N ratio and low NDF/SC ratio are preferable with regard to manure quality, but may not satisfy the nutritional requirements of producing animals, since N concentration in these diets was low and fibre concentration simultaneously high.

Excitation of Phonons in Solids and Nanostructures by Intense Laser and XUV Pulses and by Low Energy Atomic Collision

Intensive, ultrakurze Laserpulse regen Festkörper in einen Zustand an, in dem die Elektronen hohe Temperaturen erlangen, während das Gitter kalt bleibt. Die heißen Elektronen beeinflussen das sog. Laser-angeregte interatomare Potential bzw. die Potentialenergiefläche, auf der die Ionen sich bewegen. Dieses kann neben anderen ultrakurzen Prozessen zu Änderungen der Phononfrequenzen (phonon softening oder phonon hardening) führen. Viele ultrakurze strukturelle Phänomene in Festkörpern hängen bei hohen Laseranregungen von Änderungen der Phononfrequenzen bei niedrigeren Anregungen ab. Um die Laser-bedingten Änderungen des Phononenspektrums von Festkörpern beschreiben zu können, haben wir ein auf Temperatur-abhängiger Dichtefunktionaltheorie basierendes Verfahren entwickelt. Die dramatischen Änderungen nach einer Laseranregung in der Potentialenergiefläche werden durch die starke Veränderung der Zustandsdichte und der Besetzungen der Elektronen hervorgerufen. Diese Änderungen in der Zustandsdichte und den Besetzungszahlen können wir mit unserer Methode berechnen, um dann damit das Verhalten der Phononen nach einer Laseranregung zu analysieren. Auf diese Art und Weise studierten wir den Einfluss einer Anregung mit einem intensiven, ultrakurzen Laserpuls auf repräsentative Phonon Eigenmoden in Magnesium, Kupfer und Aluminium. Wir stellten dabei in manchen Gitterschwingungen entweder eine Abnahme (softening) und in anderen eine Zunahme (hardening) der Eigenfrequenz fest. Manche Moden zeigten bei Variation der Laseranregungsstärke sogar beide Verhaltensweisen. Das eine Phonon-Eigenmode ein hardening und softening zeigen kann, wird durch das Vorhandensein von van Hove Singularitäten in der elektronischen Zustandsdichte des betrachteten Materials erklärt. Für diesen Fall stellt unser Verfahren zusammen mit der Sommerfeld-Entwicklung die Eigenschaften der Festkörper Vibrationen in Verbindung mit den Laser induzierten Veränderungen in den elektronischen Besetzungen für verschiedene Phonon-eingefrorene Atomkonfigurationen. Auch die absolute Größe des softening und hardening wurde berechnet. Wir nehmen an, dass unsere Theorie Licht in die Effekte der Laseranregung von verschiedenen Materialien bringt. Außerdem studierten wir mit Hilfe von Dichtefunktionaltheorie die strukturellen Material-Eigenschaften, die durch kurze XUV Pulse induziert werden. Warme dichte Materie in Ultrakurzpuls angeregten Magnesium wurde analysiert und verglichen mit den Ergebnissen bei durch Laser Anregung bedingten Änderungen. Unter Verwendung von elektronischer-Temperatur-abhängiger Dichtefunktionaltheorie wurden die Änderungen in den Bindungseigenschaften von warmen dichten Magnesium studiert. Wir stellten dabei beide Effekte, Verstärkung und Abschwächung von Bindungen, bei jeweils verschiedenen Phonon Eigenmoden von Magnesium auf Grund von der Erzeugung von Rumpflöchern und dem Vorhandensein von heißen Elektronen fest. Die zusätzliche Erzeugung von heißen Elektronen führt zu einer Änderung der Bindungscharakteristik, die der Änderung, die durch die bereits vorhandenen Rumpflöcher hervorgerufen wurde, entgegen wirkt. Die thermischen Eigenschaften von Nanostrukturen sind teilweise sehr wichtig für elektronische Bauteile. Wir studierten hier ebenfalls den Effekt einer einzelnen Graphen Lage auf Kupfer. Dazu untersuchten wir mit Dichtefunktionaltheorie die strukturellen- und Schwingungseigenschaften von Graphen auf einem Kupfer Substrat. Wir zeigen, dass die schwache Wechselwirkung zwischen Graphen und Kupfer die Frequenz der aus der Ebene gerichteten akustischen Phonon Eigenmode anhebt und die Entartung zwischen den aus der Ebene gerichteten akustischen und optischen Phononen im K-Punkt des Graphen Spektrums aufhebt. Zusätzlich führten wir ab initio Berechnungen zur inelastischen Streuung eines Helium Atoms mit Graphen auf einem Kuper(111) Substrat durch. Wir berechneten dazu das Leistungsspektrum, das uns eine Idee über die verschiedenen Gitterschwingungen des Graphene-Kuper(111) Systems gibt, die durch die Kollision des Helium Atom angeregt werden. Wir brachten die Positionen der Peaks im Leistungsspektrum mit den Phonon Eigenfrequenzen, die wir aus den statischen Rechnungen erhalten haben, in Beziehung. Unsere Ergebnisse werden auch verglichen mit den Ergebnissen experimenteller Daten zur Helium Streuung an Graphen-Kupfer(111) Oberflächen.