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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.
This thesis focuses on the investigation and characterization of the surfaces and interfaces of chalcopyrite-based Cu(In,Ga)Se₂ (CIGSe) and organo-metal mixed halide perovskites, specifically CH₃NH₃PbI(₃-ᵪ)Clᵪ thin film solar cell absorbers using various x-ray and electron spectroscopies. In particular, the impact of alkali treatments on the chemical and electronic surface and near-surface structure of CIGSe absorbers is studied. For CH₃NH₃PbI(₃-ᵪ)Clᵪ the compound formation is monitored and the peculiarities of the interface formation of CH₃NH₃PbI(₃-ᵪ)Clᵪ on compact and mesoporous TiO₂ are examined.
Laboratory and synchrotron-based photoelectron spectroscopy are used to gain a depth-dependent picture of the chemical and electronic structure in the surface and near-surface region of CIGSe absorbers, focusing on the influence of NaF and NaF/KF post-deposition treatments (PDT) when compared to alkali-free CIGSe absorbers. The alkali-free and NaF-PDT absorbers show similar chemical properties, having a Cu and Ga poor surface region compared to the nominal bulk and the same chemical environment for indium and selenium. For the NaF/KF-PDT samples a K-In-Se compound is present on top of a Cu-In-Ga-Se compound, with a nanopatterned surface that is almost devoid of Cu and Ga.
Further, for the NaF-PDT sample a near-surface electronic band gap of 1.61[+0.14/-0.51] eV is derived. In contrast, a large and more gradual change towards the surface is obtained for the NaF/KF-PDT absorber exhibiting a significant band gap widening of the surface, which is in agreement with a Cu- and Ga-devoid surface region and the formation of a K-In-Se surface compound.
To in-situ monitor the compound formation of CH₃NH₃PbI(₃-ᵪ)Clᵪ on compact TiO₂ (c-TiO₂) hard x-ray photoelectron spectroscopy is used. During in-situ annealing a drop-casted layer of precursor solution on c-TiO₂ shifts in the perovskite related core levels can be observed upon reach the “transition temperature” of 80-100°C. Further the Cl signal decrease at the onset of annealing and shows a depletion in the surface region for annealing temperatures above 50°C. In addition, the chemical and electronic structure of the interface between perovskite and mesoporous TiO₂ (mp-TiO₂) or c-TiO₂ using different perovskite layer thicknesses are studied.
Stochastic modelling of biochemical reaction networks is getting more and more popular. Throughout the past decades typical biological models increased in their size and complexity, because of advances in systems and molecular biology, in particular through the high-throughput omic technologies. Here biochemical networks of different levels of detail are modelled, starting with simple chemical reactions and signal transduction networks, up to individual cells and entire organisms. This increases the demand for efficient analysis methods.
A Petri net is a mathematical modelling language for the description of concurrent behaviour of distributed systems. Its advantage is the ease of scalability of the models, which relates to the network’s state space, as well as the structure of the network itself.
In this work, we recall several stochastic simulation algorithms, e.g., exact as well as approximate methods. Furthermore, we introduce an approach to improve the efficiency of stochastic simulation for large and dense networks by a new approximate stochastic simulation algorithm called discrete-time leap method. We depict the wide range of simulative analyses of complex stochastic systems ranging from trace generation to the computation of transient solutions and steady state distributions. We set forth advanced analysis of stochastic models by means of simulative model checking. For the use of simulative model checking, we integrate the continuous stochastic (reward) logic (CS(R)L) and the probabilistic linear-time temporal logic with constraints (PLTLc). Simulative model checking has some limitations compared to the numerical methods, e.g., in principle it is possible to consider nested probabilistic formulas in CS(R)L, but not practical, since the calculation is not feasible in a reasonable period of time. In addition to the transient analysis, the steady state analysis is often of interest; therefore we have implemented two on-the-fly steady state detection methods. The first one is based on a “sample batch means” algorithm and is used in the linear-time temporal logic. The second approximates the steady state distribution and checks for convergence. We apply the aforementioned techniques to several case studies from systems biology and technical systems.
The main contributions of this thesis to scientific knowledge are the development of the discrete-time leap method for the simulation of stochastic models, the approximations of transient solutions and steady state distributions by use of stochastic simulation for stochastic models and Markov reward models, the development of an infinite time horizon model checking algorithm exploiting the steady state property for PLTLc and CSL, and the first simulative model checking algorithm for CSRL incorporating state and impulse rewards. All presented algorithms and methods are implemented in the advanced analysis tool MARCIE.
With the integration of smart objects into the Internet users should gain new possibilities to directly interact with their physical environment. This vision is called Internet of Things (IoT) and is enabled by the development of micro Internet Protocol (IP) stacks that allow one to directly connect smart objects to the Internet. IP alone cannot ensure a seamless integration because advanced services (e.g., service discovery, identity management) can only be provided at the application layer. The current development of application protocols for the IoT focuses on the Machine-to-Machine (M2M) communication and introduces specialized protocol gateways, smart object-specific code or data representations that hinder a seamless integration. This thesis deals with the seamless integration, discovery, and employment of smart objects into the current Internet infrastructure under Human-to-Machine (H2M) communication aspects by using and adapting already established protocols that have been standardized by the Internet Engineering Task Force (IETF), such as the Extensible Messaging and Presence Protocol (XMPP), Multicast DNS (mDNS), and DNS Service Discovery (DNS-SD). The proposed approach is called Chatty Things. So smart objects may become a natural part of the network making the IoT readily usable for (non-technical) users and network administrators providing them with the same level of usability that is predominant in the current Internet infrastructure.
The applicability of XMPP and mDNS/DNS-SD for smart objects has been evaluated with implementations of minimized, modular, and extensible software stacks for the IoT operating system Contiki. This includes a readily usable Application Programming Interface (API), an essential set of XMPP extension protocols, a proposal for lightweight and user-friendly event notification, a standardized bootstrapping, and a seamless fallback mechanism for ad hoc use cases when infrastructure services are failing for XMPP-driven smart objects. Furthermore, this thesis presents optimizations for the used protocols to reduce the network traffic in low data rate smart object networks (e.g., sensor-specific groups, enhanced message compression mechanisms). To sum up, this thesis shows how XMPP and mDNS/DNS-SD can be used economically on smart objects for the seamless integration with low effort into the current Internet infrastructure to enable a transparent (H2M) interaction and service discovery for the IoT.
Nanotechnologies allow for the production of completely new materials in a wide range of industries and technical fields and are also recognised as one of the most important technological sectors for the future. The growing nanotechnological industry is rapidly generating new forms of materials; however, little is known about the behaviour of these substances, in particular their particle form and their impact on different ecological systems and the life within them. Concerns have been raised about the safety and regulation of nanomaterials, following a number of studies that indicated that some nanomaterials are able to cause adverse effects on living objects. This data, as well as increasing production volumes and commercialisation, the capability of crossing biological barriers and the increased physico-chemical activities of nanoparticles, when compared to their bulk counterparts, have triggered concern (Baró et al., 2001; Kear et al., 2012) about their impacts on health and safety.
In Germany, nanoparticles, nanotechnological products, their production processes and their disposal are generally subject to the prevailing law of the German legal system, especially with respect to the authorization of equipment, permissions regarding chemicals and other product groups, and the protection of employees and the environment. With regard to nanotechnologies, however, the question arises as to whether the present legal regulations are adequate, and/or whether regulative gaps occur because of specific new products, materials or process characteristics. Accordingly, based on the analysis of the relevant state-of-the-art technology and science, and an evaluation of existing, as well as projectable, future national legislation on this matter, this work aims to identify regulative gaps in the relevant standardisation procedures and to point out possible adjustments.
Although nanomaterials are covered by the general scope of many of the existing legislative frameworks, it is often unclear if current regulation is actually applicable for specific questions of nanomaterials and their diverse applications. In particular, there is a lack of sufficient knowledge of the risks, which could lead to imbalanced legal protection against any threats that may arise. However, it is recognised that adjustments are needed, and legal amendments have been repeatedly proposed by expert committees, policymakers, industry members and non-governmental organisations (European Parliament, 2009). Nonetheless, very few revisions have been made to date, so the existing regulations are not considered adequate to deal with all kinds of nanomaterials in both the short and long term. Current legislation needs to be adapted immediately to reflect the challenges posed by current nanomaterials and their applications.
This work is devoted to the problem of liquidity that draws a lot of attention after the global financial crisis. We consider an optimization problem for a portfolio with an illiquid, a risky and a riskless liquid asset. We work in Merton’s optimal consumption framework with continuous time. The liquid part of the investment is described by a standard Black-Scholes market. The illiquid asset is sold at an exogenous random moment with prescribed distribution and generates additional liquid wealth dependent on its paper value. We show that one can consider a problem with infinite time horizon and special weight function that is characterized by the probability distribution of the liquidation time instead of a problem with an exogenous random liquidation time. Using the viscosity solution techniques, developed for the problem of optimization in presence of a random income, we prove the existence and uniqueness of the solution for the considered problem with logarithmic utility and modest restrictions on the liquidation time distribution. We find asymptotic bounds for the value function when liquidation time has exponential or Weibull distribution. We find optimal policies in a feedback form and illustrate how they differ from classical Merton’s policies. Through a Lie group analysis we find the admitted Lie algebra for a problem with general liquidation time distribution in cases of HARA and log utility functions and formulate corresponding theorems for all these cases. Using these Lie algebras we obtain reduced equations of the lower dimension for the studied three dimensional partial differential equations. Several of similar substitutions were used in other works before, whereas others are new to our knowledge. The applied method of Lie group analysis gives us the possibility to provide a complete set of non-equivalent substitutions and reduced equations that was not provided for the problem of such type so far. Further research of these equations with numerical and quantitative methods is expected to benefit from such analysis.
In arid countries, reclaimed water in irrigation is a widespread practice. Therefore, robust treatment designs are prerequisite to obtain effluent quality that conforms to the legal requirements for reuse and health standards. Vertical flow constructed wetlands (VFCWs) are attractive decentralized treatment plants in many countries and communities. VFCWs are capable of providing adequate treatment for organic and solids removal, even though there are limitations on nutrient and pathogen removal. Within this study, various VFCW systems were investigated, in Germany and Jordan, to optimize nitrogen removal using sustainable and low cost options to guarantee the safe reuse in Jordan.
In Germany at Langenreichenbach research facility, two-stage VFCWs planted (Phragmites australis) and unplanted were evaluated and modified to compare the role of plants over two years. Generally, there was no significant role of plants on the treatment performance. Both systems showed high removal efficiency for TOC, BOD5, and TSS over the study period. During the first year of the study, effluent TN concentrations ranged from 60 - 61 mg/L in both systems as a result of high effluent NO3--N concentrations (50 - 52 mg/L). In the second year, the systems were modified, adopting a saturated layer in the 1st stage to enhance denitrification. Average effluent TN concentrations were reduced to 45 mg/L in both systems. In addition, during modifications, the E.coli removal was enhanced in both systems achieving 4 log reduction instead of 2 log reduction during the first year of the study.
In Jordan at the Fuhais research facility, two VFCW systems were studied considering category-A (TN: 45 mg/L and NO3-N: 30 mg/L) in the Jordanian Standards for reuse in irrigation (JS 893/2006). Recirculating (ECO-1) and Multi-stage (ECO-2) VFCW designs have shown high removal efficiency of COD, TSS, and BOD5 over three years of monitoring. ECO-1 system combines simultaneous nitrification and denitrification by recycling portion of nitrified effluent into the recirculation tank. However, effluent TN and NO3--N concentrations were 55 and 44 mg/L, respectively, that the system conformed to the JS category-B (TN: 70 mg/L and NO3-N: 45 mg/L) during monitoring phase. Therefore, ECO-1 was modified by installing plastic media in the recirculation tank that attached growth increases the abundance and activity of microorganisms. TN concentration was reduced effectively of 40 mg/L, conforming to the JS category-A, whereas, NO3--N concentration was reduced to 37 mg/L, conforming to the JS category-B. However, over the study period, E.coli concentrations were conformed to the JS category-C (more than 1000 MPN/100 mL).
ECO-2 consists of two unsaturated VFCWs in series; single-pass unplanted filter followed by planted filter (Phragmites australis). E.coli removal was relatively high before modification that the effluent conformed to the JS (category-B: 1000 MPN/100 mL), achieving 4.4 log reduction. The effluent TN and NO3--N concentrations did not conform to the JS of 77 and 76 mg/L, respectively, due to insufficiency of carbon source to promote denitrification (high BOD5 removal) during monitoring phase of the study. Thus, ECO-2 was modified adopting raw wastewater step-feeding strategy that a specific volume of raw wastewater was mixed with 1st stage effluent in the mixing tank. TN and NO3--N concentrations were reduced to 52 and 50 mg/L, respectively; conforming to the JS category-B. Whereas, E.coli removal was influenced by E.coli ingress from raw step-feeding, achieving 3.5 log reduction, conforming to the JS category-C.
The short-term impact of irrigation with different water quality and quantity was investigated at the Fuhais site. Soil physicochemical and biological properties in three parallel experimental reuse plots were investigated. The plots were cultivated with lemon trees and were irrigated via a subsurface irrigation system. Moreover, each plot was divided into two subparts (A and B) whereby one part received 11 mm/day of irrigation water and the other received 6 mm/day. Using treated effluent and tap water showed the same trend of increased soli salinity (ECs). Significant difference in ECs, SAR, Mg+2, Ca+2, and Na+ were observed at 0-20 cm as a result of high evaporation and capillary rise that increased salts accumulation in the topsoil. However, using more water reduced the salts accumulation in sub soil layers due to continuous leaching. Whereas, results showed no significant variation in soil texture, structure, moisture, and infiltration rate among reuse plots and subparts. Additionally, results revealed an absence of total coliform, fecal coliform, and E.coli in the irrigated soils, indicating the effectiveness of using subsurface irrigation as a disinfection step for reuse.
On the applicability of short key asymmetric cryptography in low power wireless sensor networks
(2016)
The growing popularity of Wireless Sensor Networks (WSN) makes the spectrum of their applications very wide. A great number of the application areas like health monitoring or military applications require a high level of security and dependability from the wireless sensor network. Solving these issues can be supported by providing cryptographic solutions into WSN applications. Since the WSNs mainly consist of low power devices, cryptographic solutions ideal for WSNs should provide computationally lightweight security mechanisms producing small data packets and ensuring confidentiality. Cryptographic mechanisms that have both these features are considered in this thesis, which main objective is the analysis of the applicability of the short key elliptic curve cryptography in WSN environments. Reduced key lengths require modification of the standard ECC security algorithms to provide authentication and also a novel solution for a cryptographic secure pseudo-random number generator. The proposed solution is based on the standard ECC, but it differs in several aspects. The main difference is that the parameters of the used elliptic curve have to be kept secret. This is due to the fact that solving the Discreet Logarithm Problem (DLP) for such short parameters can be done in short time. Additionally, using shorter parameters for the underlying elliptic curves excludes also the use of standard hash functions, what mainly influences the mechanisms for generating the digital signature. Hash functions require large input values and produce relatively large output data that is inapplicable in the shortECC environment. Thus, within this thesis a modified version of standard Elliptic Curves Digital Signature Algorithm is proposed, which does not require any hash function. The shortECC needs pseudo-random numbers in the encryption and the digital signature protocols, but since it operates on numbers that are significantly shorter than the ones used by other cryptographic approaches, pseudo-random number generators for standard approaches are not suitable for shortECC. Thus, the new pseudo-random number generator not involving any additional hardware besides the modules available on the used test platform and operating on 32-bit long integers, is proposed. The randomness of the numbers generated by the proposed algorithm and their applicability for cryptographic purposes was evaluated using the NIST test suites. The shortECC approach was also subjected to cryptanalysis in order to proof its security and determine the circumstances and constraints for its application.
Vortrag “ICESP XIV. International Conference on Electrostatic Precipitation 2016”, Wroclaw, Polen, 19.-23.09.2016
Back corona and dust resistivity are well known topics in electrostatic precipitation. Back corona results from high dust resistivity and occurs when the field strength in the dust layer surpasses a critical value E crit, which is typically found to be in the order of 15 to 30 kV/cm. Besides the resistivity ρ, the current density is the main parameter: E = i ρ < E crit. Hence, possible actions against back corona include a reduction of ρ by dust conditioning, or a reduction of i, for example by pulsed corona operation.
Much work has been devoted to study the dependence of ρ on dust composition, temperature, humidity, adsorption layers and dust layer porosity, and a variety of different set-ups for dust resistivity measurements has been proposed. Even though some authors report a dependence of ρ on current density or field strength resp., dust resistivity is mostly seen as a material property.
However, in measurements on product dusts in the upper resistivity range, we found that dusts show extremely non-ohmic properties:
Most strikingly, resistivity may vary by several orders of magnitude with time.
Also, the experimental arrangement can change the resistivity results by orders of magnitude: When resistivity is measured with the dust layer exposed to a corona discharge (imitating the situation in a real ESP), ρ depends strongly on the layer thickness. Meanwhile the same dust does not show the strong layer thickness dependence when electrodes are placed on both sides of the dust layer, and also time effects are much less prominent.
Additional findings include that dusts that have been exposed to resistivity measurements show a high level of electrostatic charging afterwards.
An interpretation of these results may be found from the theory of semiconductors and electret materials. Accordingly, highly resistive dust layers do not contain mobile electrons. Current transport occurs only after charge carriers (free electrons or holes) have been injected from the electrodes or from a gas discharge adjacent to the surface.
When the injection process is non-symmetric (e.g. with corona discharge), the current transport through the dust layer can be dominated by charge carriers of one polarity, depending on the polarity of the corona. Some of the effects observed in experiment, namely the layer thickness effect and the current density influence, can indeed be ascribed to unipolar injection and space charge limited conduction.
The time effects can mainly be ascribed to the “deep trapping” of the charge carriers, leading to a high level of immobile space charge. As overall space charge is limited, this reduces the level of mobile space charge available for current transport. The space charge also leads to a deformation of the electric field inside the dust layer, and hence influences injection via the Schottky (thermionic field emission) mechanism.
By integrating the mechanisms of charge transport in dielectrics (injection, drift, immobilization, recombination) into the OpenFOAM® simulation package, rather realistic simulations of time-dependent resistivity are possible. The simulations also are helpful to identify the mechanisms responsible for certain types of resistivity behavior.
Guided waves hold great potential for applications in the field of ultrasonic nondestructive testing. Examples of possible applications are the ultrasonic testing and structural health monitoring of wheelset-axles as used in trains. Depending on the particular type, these axles can be described as either thick cylindrical rods or thick walled hollow cylinders with varying thickness.
Wheelset-axles are safety relevant components that have to be inspected on a regular basis. The use of guided waves would allow a full inspection while accessing only the front faces of the axle, thus potentially speeding up the inspection procedure. In order to develop such an inspection technique, however, detailed knowledge of wave propagation through the axle is required.
Established mesh-based procedures, like the finite element method, could be used to simulate guided wave propagation in such structures. However, due to the size of the axle itself and the comparatively fine mesh that is dictated by the wavelengths usually applied in ultrasonic testing, these mesh-based procedures would be very expensive in terms of computation times. The multimodal approach seems to be a very promising alternative that can be expected to provide results significantly faster.
The multimodal method uses the guided wave modes of a corresponding waveguide with a constant cross-section as basis in which the local sound field at any given position in a waveguide with varying thickness can be expressed. Thereby the numerical effort is reduced to solving the one dimensional differential equations that govern the evolution of the coefficients in the mode spectrum along the waveguide. Once the sound field has been calculated, a time dependence can easily be included, which allows the simulation of pulse propagation through the waveguide.
In this thesis, the multimodal approach, as described for the calculation of Lamb-waves in plates with non-constant thickness, is extended to other types of elastic waveguides such as cylindrical rods and thick walled hollow cylinders. For the sake of simplicity, investigations are restricted to axially symmetric wave modes. The results obtained with the multimodal approach are validated against FEM-simulations. It is shown that the multimodal method potentially holds a great advantage in terms of computation time over commercially available software based on the finite element method. Finally, the multimodal method is evaluated with respect to possible future applications on wheelset-axles.