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This thesis investigates the constrained form of the spherical Minimax location problem and the spherical Weber location problem. Specifically, we consider the problem of locating a new facility on the surface of the unit sphere in the presence of convex spherical polygonal restricted regions and forbidden regions such that the maximum weighted distance from the new facility on the surface of the unit sphere to m existing facilities is minimized and the sum of the weighted distance from the new facility on the surface of the unit sphere to m existing facilities is minimized. It is assumed that a forbidden region is an area on the surface of the unit sphere where travel and facility location are not permitted and that distance is measured using the great circle arc distance. We represent a polynomial time algorithm for the spherical Minimax location problem for the special case where all the existing facilities are located on the surface of a hemisphere. Further, we have developed algorithms for spherical Weber location problem using barrier distance on a hemisphere as well as on the unit sphere.

The present thesis deals with a novel approach to increase the resource usage in digital communications. In digital communication systems, each information bearing data symbol is associated to a waveform which is transmitted over a physical medium. The time or frequency separations among the waveforms associated to the information data have always been chosen to avoid or limit the interference among them. By doing so, n the presence of a distortionless ideal channel, a single receive waveform is affected as little as possible by the presence of the other waveforms. The conditions necessary to meet the absence of any interference among the waveforms are well known and consist of a relationship between the minimum time separation among the waveforms and their bandwidth occupation or, equivalently, the minimum frequency separation and their time occupation. These conditions are referred to as Nyquist assumptions. The key idea of this work is to relax the Nyquist assumptions and to transmit with a time and/or frequency separation between the waveforms smaller than the minimum required to avoid interference. The reduction of the time and/or frequency separation generates not only an increment of the resource usage, but also a degradation in the quality of the received data. Therefore, to maintain a certain quality in the received signal, we have to increase the amount of transmitted power. We investigate the trade-off between the increment of the resource usage and the correspondent performance degradation in three different cases. The first case is the single carrier case in which all waveforms have the same spectrum, but have different temporal locations. The second one is the multi carrier case in which each waveform has its distinct spectrum and occupies all the available time. Finally, the hybrid case when each waveform has its unique time and frequency location. These different cases are framed within the general system modelling developed in the thesis so that they can be easily compared. We evaluate the potential of the key idea of the thesis by choosing a set of four possible waveforms with different characteristics. By doing so, we study the influence of the waveform characteristics in the three system configurations. We propose an interpretation of the results by modifying the well-known Shannon capacity formula and by explicitly expressing its dependency on the increment of resource usage and on the performance degradation. The results are very promising. We show that both in the case of a single carrier system with a time limited waveform and in the case of a multi-carrier system with a frequency limited waveform, the reduction of the time or frequency separation, respectively, has a positive effect on the channel capacity. The latter, depending on the actual SNR, can double or increase even more significantly.

Competing Neural Networks as Models for Non Stationary Financial Time Series -Changepoint Analysis-
(2005)

The problem of structural changes (variations) play a central role in many scientific fields. One of the most current debates is about climatic changes. Further, politicians, environmentalists, scientists, etc. are involved in this debate and almost everyone is concerned with the consequences of climatic changes. However, in this thesis we will not move into the latter direction, i.e. the study of climatic changes. Instead, we consider models for analyzing changes in the dynamics of observed time series assuming these changes are driven by a non-observable stochastic process. To this end, we consider a first order stationary Markov Chain as hidden process and define the Generalized Mixture of AR-ARCH model(GMAR-ARCH) which is an extension of the classical ARCH model to suit to model with dynamical changes. For this model we provide sufficient conditions that ensure its geometric ergodic property. Further, we define a conditional likelihood given the hidden process and a pseudo conditional likelihood in turn. For the pseudo conditional likelihood we assume that at each time instant the autoregressive and volatility functions can be suitably approximated by given Feedfoward Networks. Under this setting the consistency of the parameter estimates is derived and versions of the well-known Expectation Maximization algorithm and Viterbi Algorithm are designed to solve the problem numerically. Moreover, considering the volatility functions to be constants, we establish the consistency of the autoregressive functions estimates given some parametric classes of functions in general and some classes of single layer Feedfoward Networks in particular. Beside this hidden Markov Driven model, we define as alternative a Weighted Least Squares for estimating the time of change and the autoregressive functions. For the latter formulation, we consider a mixture of independent nonlinear autoregressive processes and assume once more that the autoregressive functions can be approximated by given single layer Feedfoward Networks. We derive the consistency and asymptotic normality of the parameter estimates. Further, we prove the convergence of Backpropagation for this setting under some regularity assumptions. Last but not least, we consider a Mixture of Nonlinear autoregressive processes with only one abrupt unknown changepoint and design a statistical test that can validate such changes.

In conventional radio communication systems, the system design generally starts from the transmitter (Tx), i.e. the signal processing algorithm in the transmitter is a priori selected, and then the signal processing algorithm in the receiver is a posteriori determined to obtain the corresponding data estimate. Therefore, in these conventional communication systems, the transmitter can be considered the master and the receiver can be considered the slave. Consequently, such systems can be termed transmitter (Tx) oriented. In the case of Tx orientation, the a priori selected transmitter algorithm can be chosen with a view to arrive at particularly simple transmitter implementations. This advantage has to be countervailed by a higher implementation complexity of the a posteriori determined receiver algorithm. Opposed to the conventional scheme of Tx orientation, the design of communication systems can alternatively start from the receiver (Rx). Then, the signal processing algorithm in the receiver is a priori determined, and the transmitter algorithm results a posteriori. Such an unconventional approach to system design can be termed receiver (Rx) oriented. In the case of Rx orientation, the receiver algorithm can be a priori selected in such a way that the receiver complexity is minimum, and the a posteriori determined transmitter has to tolerate more implementation complexity. In practical communication systems the implementation complexity corresponds to the weight, volume, cost etc of the equipment. Therefore, the complexity is an important aspect which should be taken into account, when building practical communication systems. In mobile radio communication systems, the complexity of the mobile terminals (MTs) should be as low as possible, whereas more complicated implementations can be tolerated in the base station (BS). Having in mind the above mentioned complexity features of the rationales Tx orientation and Rx orientation, this means that in the uplink (UL), i.e. in the radio link from the MT to the BS, the quasi natural choice would be Tx orientation, which leads to low cost transmitters at the MTs, whereas in the downlink (DL), i.e. in the radio link from the BS to the MTs, the rationale Rx orientation would be the favorite alternative, because this results in simple receivers at the MTs. Mobile radio downlinks with the rationale Rx orientation are considered in the thesis. Modern mobile radio communication systems are cellular systems, in which both the intracell and intercell interferences exist. These interferences are the limiting factors for the performance of mobile radio systems. The intracell interference can be eliminated or at least reduced by joint signal processing with consideration of all the signals in the considered cell. However such joint signal processing is not feasible for the elimination of intercell interference in practical systems. Knowing that the detrimental effect of intercell interference grows with its average energy, the transmit energy radiated from the transmitter should be as low as possible to keep the intercell interference low. Low transmit energy is required also with respect to the growing electro-phobia of the public. The transmit energy reduction for multi-user mobile radio downlinks by the rationale Rx orientation is dealt with in the thesis. Among the questions still open in this research area, two questions of major importance are considered here. MIMO is an important feature with respect to the transmit power reduction of mobile radio systems. Therefore, first questionconcerns the linear Rx oriented transmission schemes combined with MIMO antenna structures. The investigations of the MIMO benefit on the linear Rx oriented transmission schemes are studied in the thesis. Utilization of unconventional multiply connected quantization schemes at the receiver has also great potential to reduce the transmit energy. Therefore, the second question considers the designing of non-linear Rx oriented transmission schemes combined with multiply connected quantization schemes.

The thesis is focused on modelling and simulation of a Joint Transmission and Detection Integrated Network (JOINT), a novel air interface concept for B3G mobile radio systems. Besides the utilization of the OFDM transmission technique, which is a promising candidate for future mobile radio systems, and of the duplexing scheme time division duplexing (TDD), the subdivision of the geographical domain to be supported by mobile radio communications into service areas (SAs) is a highlighted concept of JOINT. A SA consists of neighboring sub-areas, which correspond to the cells of conventional cellular systems. The signals in a SA are jointly processed in a Central Unit (CU) in each SA. The CU performs joint channel estimation (JCE) and joint detection (JD) in the form of the receive-zero-forcing (RxZF) Filter for the uplink (UL) transmission and joint transmission (JT) in the form of the transmit-zero-forcing (TxZF) Filter for the downlink (DL) transmission. By these algorithms intra-SA multiple access interference (MAI) can be eliminated within the limits of the used model so that unbiased data estimates are obtained, and most of the computational effort is moved from mobile terminals (MTs) to the CU so that the MTs can do with low complexity. A simulation chain of JOINT has been established in the software MLDesigner by the author based on time discrete equivalent lowpass modelling. In this simulation chain, all key functionalities of JOINT are implemented. The simulation chain is designed for link level investigations. A number of channel models are implemented both for the single-SA scenario and the multiple-SA scenario so that the system performance of JOINT can be comprehensively studied. It is shown that in JOINT a duality or a symmetry of the MAI elimination in the UL and in the DL exists. Therefore, the typical noise enhancement going along with the MAI elimination by JD and JT, respectively, is the same in both links. In the simulations also the impact of channel estimation errors on the system performance is studied. In the multiple-SA scenario, due to the existence of the inter-SA MAI, which cannot be suppressed by the algorithms of JD and JT, the system performance in terms of the average bit error rate (BER) and the BER statistics degrades. A collection of simulation results show the potential of JOINT with respect to the improvement of the system performance and the enhancement of the spectrum e±ciency as compared to conventional cellular systems.

Under physiological conditions oxygen is constantly being converted to reactive oxygen intermediates, in mitochondria, peroxisomes, cytochrome p450 systems, macrophages, neutrophils and in plasma membranes. These reactive oxygen species (ROS) are toxic and therefore alter cell integrity leading to cell damage. To protect itself against this toxic effect of ROS, living systems have developed defence systems that scavenge ROS formation. These systems include some enzymes, transporting proteins and small antioxidant molecules for instance vitamin C and E. This thesis describes a study on the antioxidant chemistry and activity of vitamin C in vivo and in vitro systems using ESR spectroscopy. Also, a new method was designed to label ascorbic acid with a fluorescent marker. Moreover, some important criteria were considered for the evaluation and quantification of ascorbyl radicals in human blood plasma using two types of ESR spectrometers.

In this dissertation a model of melt spinning (by Doufas, McHugh and Miller) has been investigated. The model (DMM model) which takes into account effects of inertia, air drag, gravity and surface tension in the momentum equation and heat exchange between air and fibre surface, viscous dissipation and crystallization in the energy equation also has a complicated coupling with the microstructure. The model has two parts, before onset of crystallization (BOC) and after onset of crystallization (AOC) with the point of onset of crystallization as the unknown interface. Mathematically the model has been formulated as a Free boundary value problem. Changes have been introduced in the model with respect to the air drag and an interface condition at the free boundary. The mathematical analysis of the nonlinear, coupled free boundary value problem shows that the solution of this problem depends heavily on initial conditions and parameters which renders the global analysis impossible. But by defining a physically acceptable solution, it is shown that for a more restricted set of initial conditions if a unique solution exists for IVP BOC then it is physically acceptable. For this the important property of the positivity of the conformation tensor variables has been proved. Further it is shown that if a physically acceptable solution exists for IVP BOC then under certain conditions it also exists for IVP AOC. This gives an important relation between the initial conditions of IVP BOC and the existence of a physically acceptable solution of IVP AOC. A new investigation has been done for the melt spinning process in the framework of classical mechanics. A Hamiltonian formulation has been done for the melt spinning process for which appropriate Poisson brackets have been derived for the 1-d, elongational flow of a viscoelastic fluid. From the Hamiltonian, cross sectionally averaged balance mass and momentum equations of melt spinning can be derived along with the microstructural equations. These studies show that the complicated problem of melt spinning can also be studied under the framework of classical mechanics. This work provides the basic groundwork on which further investigations on the dynamics of a fibre could be carried out. The Free boundary value problem has been solved numerically using shooting method. Matlab routines have been used to solve the IVPs arising in the problem. Some numerical case studies have been done to study the sensitivity of the ODE systems with respect to the initial guess and parameters. These experiments support the analysis done and throw more light on the stiff nature and ill posedness of the ODE systems. To validate the model, simulations have been performed on sets of data provided by the company. Comparison of numerical results (axial velocity profiles) has been done with the experimental profiles provided by the company. Numerical results have been found to be in excellent agreement with the experimental profiles.

Since its invention by Sir Allistair Pilkington in 1952, the float glass process has been used to manufacture long thin flat sheets of glass. Today, float glass is very popular due to its high quality and relatively low production costs. When producing thinner glass the main concern is to retain its optical quality, which can be deteriorated during the manufacturing process. The most important stage of this process is the floating part, hence is considered to be responsible for the loss in the optical quality. A series of investigations performed on the finite products showed the existence of many short wave patterns, which strongly affect the optical quality of the glass. Our work is concerned with finding the mechanism for wave development, taking into account all possible factors. In this thesis, we model the floating part of the process by an theoretical study of the stability of two superposed fluids confined between two infinite plates and subjected to a large horizontal temperature gradient. Our approach is to take into account the mixed convection effects (viscous shear and buoyancy), neglecting on the other hand the thermo-capillarity effects due to the length of our domain and the presence of a small stabilizing vertical temperature gradient. Both fluids are treated as Newtonian with constant viscosity. They are immiscible, incompressible, have very different properties and have a free surface between them. The lower fluid is a liquid metal with a very small kinematic viscosity, whereas the upper fluid is less dense. The two fluids move with different velocities: the speed of the upper fluid is imposed, whereas the lower fluid moves as a result of buoyancy effects. We examine the problem by means of small perturbation analysis, and obtain a system of two Orr-Sommerfeld equations coupled with two energy equations, and general interface and boundary conditions. We solve the system analytically in the long- and short- wave limit, by using asymptotic expansions with respect to the wave number. Moreover, we write the system in the form of a general eigenvalue problem and we solve the system numerically by using Chebyshev spectral methods for fluid dynamics. The results (both analytical and numerical) show the existence of the small-amplitude travelling waves, which move with constant velocity for wave numbers in the intermediate range. We show that the stability of the system is ensured in the long wave limit, a fact which is in agreement with the real float glass process. We analyze the stability for a wide range of wave numbers, Reynolds, Weber and Grashof number, and explain the physical implications on the dynamics of the problem. The consequences of the linear stability results are discussed. In reality in the float glass process, the temperature strongly influences the viscosity of both molten metal and hot glass, which will have direct consequences on the stability of the system. We investigate the linear stability of two superposed fluids with temperature dependent viscosities by considering a different model for the viscosity dependence of each fluid. Although, the temperature-viscosity relationships for glass and metal are more complex than those used in our computations, our intention is to emphasize the effects of this dependence on the stability of the system. It is known from the literature that in the case of one fluid, the heat, which causes viscosity to decrease along the domain, usually destabilizes the flow. For the two superposed fluids problem we investigate this behaviour and discuss the consequences of the linear stability in this new case.

Non-commutative polynomial algebras appear in a wide range of applications, from quantum groups and theoretical physics to linear differential and difference equations. In the thesis, we have developed a framework, unifying many important algebras in the classes of \(G\)- and \(GR\)-algebras and studied their ring-theoretic properties. Let \(A\) be a \(G\)-algebra in \(n\) variables. We establish necessary and sufficient conditions for \(A\) to have a Poincar'e-Birkhoff-Witt (PBW) basis. Further on, we show that besides the existence of a PBW basis, \(A\) shares some other properties with the commutative polynomial ring \(\mathbb{K}[x_1,\ldots,x_n]\). In particular, \(A\) is a Noetherian integral domain of Gel'fand-Kirillov dimension \(n\). Both Krull and global homological dimension of \(A\) are bounded by \(n\); we provide examples of \(G\)-algebras where these inequalities are strict. Finally, we prove that \(A\) is Auslander-regular and a Cohen-Macaulay algebra. In order to perform symbolic computations with modules over \(GR\)-algebras, we generalize Gröbner bases theory, develop and respectively enhance new and existing algorithms. We unite the most fundamental algorithms in a suite of applications, called "Gröbner basics" in the literature. Furthermore, we discuss algorithms appearing in the non-commutative case only, among others two-sided Gröbner bases for bimodules, annihilators of left modules and operations with opposite algebras. An important role in Representation Theory is played by various subalgebras, like the center and the Gel'fand-Zetlin subalgebra. We discuss their properties and their relations to Gröbner bases, and briefly comment some aspects of their computation. We proceed with these subalgebras in the chapter devoted to the algorithmic study of morphisms between \(GR\)-algebras. We provide new results and algorithms for computing the preimage of a left ideal under a morphism of \(GR\)-algebras and show both merits and limitations of several methods that we propose. We use this technique for the computation of the kernel of a morphism, decomposition of a module into central characters and algebraic dependence of pairwise commuting elements. We give an algorithm for computing the set of one-dimensional representations of a \(G\)-algebra \(A\), and prove, moreover, that if the set of finite dimensional representations of \(A\) over a ground field \(K\) is not empty, then the homological dimension of \(A\) equals \(n\). All the algorithms are implemented in a kernel extension Plural of the computer algebra system Singular. We discuss the efficiency of computations and provide a comparison with other computer algebra systems. We propose a collection of benchmarks for testing the performance of algorithms; the comparison of timings shows that our implementation outperforms all of the modern systems with the combination of both broad functionality and fast implementation. In the thesis, there are many new non-trivial examples, and also the solutions to various problems, arising in different fields of mathematics. All of them were obtained with the developed theory and the implementation in Plural, most of them are treated computationally in this thesis for the first time.

We work in the setting of time series of financial returns. Our starting point are the GARCH models, which are very common in practice. We introduce the possibility of having crashes in such GARCH models. A crash will be modeled by drawing innovations from a distribution with much mass on extremely negative events, while in ''normal'' times the innovations will be drawn from a normal distribution. The probability of a crash is modeled to be time dependent, depending on the past of the observed time series and/or exogenous variables. The aim is a splitting of risk into ''normal'' risk coming mainly from the GARCH dynamic and extreme event risk coming from the modeled crashes. We will present several incarnations of this modeling idea and give some basic properties like the conditional first and second moments. For the special case that we just have an ARCH dynamic we can establish geometric ergodicity and, thus, stationarity and mixing conditions. Also in the ARCH case we formulate (quasi) maximum likelihood estimators and can derive conditions for consistency and asymptotic normality of the parameter estimates. In a special case of genuine GARCH dynamic we are able to establish L_1-approximability and hence laws of large numbers for the processes itself. We can formulate a conditional maximum likelihood estimator in this case, but cannot completely establish consistency for them. On the practical side we look for the outcome of estimating models with genuine GARCH dynamic and compare the result to classical GARCH models. We apply the models to Value at Risk estimation and see that in comparison to the classical models many of ours seem to work better although we chose the crash distributions quite heuristically.

This thesis deals with the development of thermoplastic polyolefin elastomers using recycled polyolefins and ground tyre rubber (GTR). The disposal of worn tyres and their economic recycling mean a great challenge nowadays. Material recycling is a preferred way in Europa owing to legislative actions and ecological arguments. This first step with worn tyres is already done in this direc-tion as GTR is available in different fractions in guaranteed quality. As the traditional applications of GTR are saturated, there is a great demand for new, value-added products containing GTR. So, the objective of this work was to convert GTR by reac-tive blending with polyolefins into thermoplastic elastomers (TPE) of suitable me-chanical and rheological properties. It has been established that bituminous reclamation of GTR prior to extrusion melt compounding with polyolefins is a promising way of TPE production. By this way the sol-content (acetone soluble fraction) of the GTR increases and the GTR particles can be better incorporated in the corresponding polyolefin matrix. The adhesion be-tween GTR and matrix is given by molecular intermingling in the resulting interphase. GTR particles of various production and mean particle size were involved in this study. As polyolefins recycled low-density polyethylene (LDPE), recycled high-density polyethylene (HDPE) and polypropylene (PP) were selected. First, the opti-mum conditions for the GTR reclamation in bitumen were established (160 °C < T < 180 °C; time ca. 4 hours). Polyolefin based TPEs were produced after GTR reclamation in extrusion compounding. Their mechanical (tensile behaviour, set properties), thermal (dynamic-mechanical thermal analysis, differential scanning calorimetry) and rheological properties (both in low- and high-shear rates ) were determined. The PE-based blends contained an ethylene/propylene/diene (EPDM) rubber as compatibilizer and their composition was as follows: PE/EPDM/GTR:bitumen = 50/25/25:25. The selected TPEs met the most important criterion, i.e. elongation at break > 100 %; compression set < 50%. The LDPE-based TPE (TPE(LDPE)) showed better me-chanical performance compared to the TPE(HDPE). This was assigned to the higher crystallinity of the HDPE. The PP-based blends of the compositions PP/(GTR-bitumen) 50/50 and 25/75, whereby the ratio of GTR/bitumen was 60/40, outperformed those containing non-reclaimed GTR. The related blends showed also a better compatibility with a PP-based commercial thermoplastic dynamic vulcanizate (TDV). Surprisingly, the mean particle size of the GTR, varied between < 0.2 and 0.4-0.7 mm, had a small effect on the mechanical properties, however somewhat larger for the rheological behaviour of the TPEs produced.

Metallocenes containing diarylethene type photochromic switches are synthesized, characterized and tested in polyolefin catalysts. Propylene polymerizations using unbridged bis(2,3-dibenzo[b]thiophen-3-yl)cyclopenta[b]thien-3-yl)zirconium dichloride/MAO (80) treated with 254nm UV irradiation produced bimodal polymer distributions by GPC. This was due to an increase in the low molecular weight fractions when the closed form of the catalyst/photoswitch was made. Comparison with similarly structured catalyst without photoisomerization properties did not produce bimodal polymer under identical conditions. Propylene polymerizations made with dimethylsilyl[(1,5-dimethyl-3-phenylcyclopenta[b]thien-6-yl)][(2,3-dibenzothien-3-yl)cyclopenta[b]thien-6-yl)]zirconium dichloride/MAO (86) with 254nm UV irradiation caused a 3 fold increase in the polymer molecular weight. Polymers made with ethylene and ethylene/hexene using (80) after UV irradiation did not show differences in measured polymer properties. Polymerizations with ethylene/ hexene mixtures using (86) had increased activity and co-monomer (hexene) incorporation with UV irradiation.

Fragmentation of tropical rain forests is pervasive and results in various modifications in the ecosystem functioning such as … It has long been noticed that the colony densities of a dominant herbivore in the neotropics - leaf-cutting ant (LCA) - increase in fragmentation-related habitats like forest edges and small fragments, however the reasons for this increase are not clear. The aim of the study was to test the hypothesis that bottom-up control of LCA populations is less effective in fragmented compared to continuous forests and thus explains the increase in LCA colony densities in these habitats. In order to test for less effective bottom-up control, I proposed four working hypotheses. I hypothesized that LCA colonies in fragmented habitats (1) find more palatable vegetation due to low plant defences, (2) forage on few dominant species resulting in a narrow diet breadth, (3) possess small foraging areas and (4) increase herbivory rate at the colony level. The study was conducted in the remnants of the Atlantic rainforest in NE Brazil. Two fragmentation-related forest habitats were included: the edge and a 3500-ha continuous forest and the interior of the 50-ha forest fragment. The interior of the continuous forest served as a control habitat for the study. All working hypotheses can be generally accepted. The results indicate that the abundance of LCA host plant species in the habitats created by forest fragmentation along with weaker chemical defense of those species (especially the lack of terpenoids) allow ants to forage predominantly on palatable species and thus reduce foraging costs on other species. This is supported by narrower ant diet breadth in these habitats. Similarly, small foraging areas in edge habitats and in small forest fragments indicate that there ants do not have to go far to find the suitable host species and thus they save foraging costs. Increased LCA herbivory rates indicate that the damages (i.e., amount of harvested foliage) caused by LCA are more important in fragmentation-related habitats which are more vulnerable to LCA herbivory due to the high availability of palatable plants and a low total amount of foliage (LAI). (1) Few plant defences, (2) narrower ant diet breadth, (3) reduced colony foraging areas, and (4) increased herbivory rates, clearly indicate a weaker bottom-up control for LCA in fragmented habitats. Weak bottom-up control in the fragmentation-related habitats decreases the foraging costs of a LCA colony in these habitats and the colonies might use the surplus of energy resulting from reduced foraging costs to increase the colony growth, the reproduction and turnover. If correct, this explains why fragmented habitats support more LCA colonies at a given time compared to continuous forest habitats. Further studies are urgently needed to estimate LCA colony growth and turnover rates. There are indices that edge effects of forest fragmentation might be more responsible in regulating LCA populations than area or isolation effects. This emphasizes the need to conserve big forest fragments not to fall below a critical size and retain their regular shape. Weak bottom-up control of LCA populations has various consequences on forested ecosystems. I suggest a loop between forest fragmentation and LCA population dynamics: the increased LCA colony densities, along with lower bottom-up control increase LCA herbivory pressure on the forest and thus inevitably amplify the deleterious effects of fragmentation. These effects include direct consequences of leaf removal by ants and various indirect effects on ecosystem functioning. This study contributes to our understanding of how primary fragmentation effects, via the alteration of trophic interactions, may translate into higher order effects on ecosystem functions.

Automated theorem proving is a search problem and, by its undecidability, a very difficult one. The challenge in the development of a practically successful prover is the mapping of the extensively developed theory into a program that runs efficiently on a computer. Starting from a level-based system model for automated theorem provers, in this work we present different techniques that are important for the development of powerful equational theorem provers. The contributions can be divided into three areas: Architecture. We present a novel prover architecture that is based on a set-based compression scheme. With moderate additional computational costs we achieve a substantial reduction of the memory requirements. Further wins are architectural clarity, the easy provision of proof objects, and a new way to parallelize a prover which shows respectable speed-ups in practice. The compact representation paves the way to new applications of automated equational provers in the area of verification systems. Algorithms. To improve the speed of a prover we need efficient solutions for the most time-consuming sub-tasks. We demonstrate improvements of several orders of magnitude for two of the most widely used term orderings, LPO and KBO. Other important contributions are a novel generic unsatisfiability test for ordering constraints and, based on that, a sufficient ground reducibility criterion with an excellent cost-benefit ratio. Redundancy avoidance. The notion of redundancy is of central importance to justify simplifying inferences which are used to prune the search space. In our experience with unfailing completion, the usual notion of redundancy is not strong enough. In the presence of associativity and commutativity, the provers often get stuck enumerating equations that are permutations of each other. By extending and refining the proof ordering, many more equations can be shown redundant. Furthermore, our refinement of the unfailing completion approach allows us to use redundant equations for simplification without the need to consider them for generating inferences. We describe the efficient implementation of several redundancy criteria and experimentally investigate their influence on the proof search. The combination of these techniques results in a considerable improvement of the practical performance of a prover, which we demonstrate with extensive experiments for the automated theorem prover Waldmeister. The progress achieved allows the prover to solve problems that were previously out of reach. This considerably enhances the potential of the prover and opens up the way for new applications.

This thesis contains the mathematical treatment of a special class of analog microelectronic circuits called translinear circuits. The goal is to provide foundations of a new coherent synthesis approach for this class of circuits. The mathematical methods of the suggested synthesis approach come from graph theory, combinatorics, and from algebraic geometry, in particular symbolic methods from computer algebra. Translinear circuits form a very special class of analog circuits, because they rely on nonlinear device models, but still allow a very structured approach to network analysis and synthesis. Thus, translinear circuits play the role of a bridge between the "unknown space" of nonlinear circuit theory and the very well exploited domain of linear circuit theory. The nonlinear equations describing the behavior of translinear circuits possess a strong algebraic structure that is nonetheless flexible enough for a wide range of nonlinear functionality. Furthermore, translinear circuits offer several technical advantages like high functional density, low supply voltage and insensitivity to temperature. This unique profile is the reason that several authors consider translinear networks as the key to systematic synthesis methods for nonlinear circuits. The thesis proposes the usage of a computer-generated catalog of translinear network topologies as a synthesis tool. The idea to compile such a catalog has grown from the observation that on the one hand, the topology of a translinear network must satisfy strong constraints which severely limit the number of "admissible" topologies, in particular for networks with few transistors, and on the other hand, the topology of a translinear network already fixes its essential behavior, at least for static networks, because the so-called translinear principle requires the continuous parameters of all transistors to be the same. Even though the admissible topologies are heavily restricted, it is a highly nontrivial task to compile such a catalog. Combinatorial techniques have been adapted to undertake this task. In a catalog of translinear network topologies, prototype network equations can be stored along with each topology. When a circuit with a specified behavior is to be designed, one can search the catalog for a network whose equations can be matched with the desired behavior. In this context, two algebraic problems arise: To set up a meaningful equation for a network in the catalog, an elimination of variables must be performed, and to test whether a prototype equation from the catalog and a specified equation of desired behavior can be "matched", a complex system of polynomial equations must be solved, where the solutions are restricted to a finite set of integers. Sophisticated algorithms from computer algebra are applied in both cases to perform the symbolic computations. All mentioned algorithms have been implemented using C++, Singular, and Mathematica, and are successfully applied to actual design problems of humidity sensor circuitry at Analog Microelectronics GmbH, Mainz. As result of the research conducted, an exhaustive catalog of all static formal translinear networks with at most eight transistors is available. The application for the humidity sensor system proves the applicability of the developed synthesis approach. The details and implementations of the algorithms are worked out only for static networks, but can easily be adopted for dynamic networks as well. While the implementation of the combinatorial algorithms is stand-alone software written "from scratch" in C++, the implementation of the algebraic algorithms, namely the symbolic treatment of the network equations and the match finding, heavily rely on the sophisticated Gröbner basis engine of Singular and thus on more than a decade of experience contained in a special-purpose computer algebra system. It should be pointed out that the thesis contains the new observation that the translinear loop equations of a translinear network are precisely represented by the toric ideal of the network's translinear digraph. Altogether, this thesis confirms and strengthenes the key role of translinear circuits as systematically designable nonlinear circuits.

In this thesis we have discussed the problem of decomposing an integer matrix \(A\) into a weighted sum \(A=\sum_{k \in {\mathcal K}} \alpha_k Y^k\) of 0-1 matrices with the strict consecutive ones property. We have developed algorithms to find decompositions which minimize the decomposition time \(\sum_{k \in {\mathcal K}} \alpha_k\) and the decomposition cardinality \(|\{ k \in {\mathcal K}: \alpha_k > 0\}|\). In the absence of additional constraints on the 0-1 matrices \(Y^k\) we have given an algorithm that finds the minimal decomposition time in \({\mathcal O}(NM)\) time. For the case that the matrices \(Y^k\) are restricted to shape matrices -- a restriction which is important in the application of our results in radiotherapy -- we have given an \({\mathcal O}(NM^2)\) algorithm. This is achieved by solving an integer programming formulation of the problem by a very efficient combinatorial algorithm. In addition, we have shown that the problem of minimizing decomposition cardinality is strongly NP-hard, even for matrices with one row (and thus for the unconstrained as well as the shape matrix decomposition). Our greedy heuristics are based on the results for the decomposition time problem and produce better results than previously published algorithms.

Within the last decades, a remarkable development in materials science took place -- nowadays, materials are not only constructed for the use of inert structures but rather designed for certain predefined functions. This innovation was accompanied with the appearance of smart materials with reliable recognition, discrimination and capability of action as well as reaction. Even though ferroelectric materials serve smartly in real applications, they also possess several restrictions at high performance usage. The behavior of these materials is almost linear under the action of low electric fields or low mechanical stresses, but exhibits strong non-linear response under high electric fields or mechanical stresses. High electromechanical loading conditions result in a change of the spontaneous polarization direction with respect to individual domains, which is commonly referred to as domain switching. The aim of the present work is to develop a three-dimensional coupled finite element model, to study the rate-independent and rate-dependent behavior of piezoelectric materials including domain switching based on a micromechanical approach. The proposed model is first elaborated within a two-dimensional finite element setting for piezoelectric materials. Subsequently, the developed two-dimensional model is extended to the three-dimensional case. This work starts with developing a micromechanical model for ferroelectric materials. Ferroelectric materials exhibit ferroelectric domain switching, which refers to the reorientation of domains and occurs under purely electrical loading. For the simulation, a bulk piezoceramic material is considered and each grain is represented by one finite element. In reality, the grains in the bulk ceramics material are randomly oriented. This property is taken into account by applying random orientation as well as uniform distribution for individual elements. Poly-crystalline ferroelectric materials at un-poled virgin state can consequently be characterized by randomly oriented polarization vectors. Energy reduction of individual domains is adopted as a criterion for the initiation of domain switching processes. The macroscopic response of the bulk material is predicted by classical volume-averaging techniques. In general, domain switching does not only depend on external loads but also on neighboring grains, which is commonly denoted as the grain boundary effect. These effects are incorporated into the developed framework via a phenomenologically motivated probabilistic approach by relating the actual energy level to a critical energy level. Subsequently, the order of the chosen polynomial function is optimized so that simulations nicely match measured data. A rate-dependent polarization framework is proposed, which is applied to cyclic electrical loading at various frequencies. The reduction in free energy of a grain is used as a criterion for the onset of the domain switching processes. Nucleation in new grains and propagation of the domain walls during domain switching is modeled by a linear kinetics theory. The simulated results show that for increasing loading frequency the macroscopic coercive field is also increasing and the remanent polarization increases at lower loading amplitudes. The second part of this work is focused on ferroelastic domain switching, which refers to the reorientation of domains under purely mechanical loading. Under sufficiently high mechanical loading, however, the strain directions within single domains reorient with respect to the applied loading direction. The reduction in free energy of a grain is used as a criterion for the domain switching process. The macroscopic response of the bulk material is computed for the hysteresis curve (stress vs strain) whereby uni-axial and quasi-static loading conditions are applied on the bulk material specimen. Grain boundary effects are addressed by incorporating the developed probabilistic approach into this framework and the order of the polynomial function is optimized so that simulations match measured data. Rate dependent domain switching effects are captured for various frequencies and mechanical loading amplitudes by means of the developed volume fraction concept which relates the particular time interval to the switching portion. The final part of this work deals with ferroelectric and ferroelastic domain switching and refers to the reorientation of domains under coupled electromechanical loading. If this free energy for combined electromechanical loading exceeds the critical energy barrier elements are allowed to switch. Firstly, hysteresis and butterfly curves under purely electrical loading are discussed. Secondly, additional mechanical loads in axial and lateral directions are applied to the specimen. The simulated results show that an increasing compressive stress results in enlarged domain switching ranges and that the hysteresis and butterfly curves flatten at higher mechanical loading levels.

This thesis aims at an overall improvement of the diffusion coefficient predictions. For this reason the theoretical determination of diffusion, viscosity, and thermodynamics in liquid systems is discussed. Furthermore, the experimental determination of diffusion coefficients is also part of this work. All investigations presented are carried out for organic binary liquid mixtures. Diffusion coefficient data of 9 highly nonideal binary mixtures are reported over the whole concentration range at various temperatures, (25, 30, and 35) °C. All mixtures investigated in a Taylor dispersion apparatus consist of an alcohol (ethanol, 1-propanol, or 1-butanol) dissolved in hexane, cyclohexane, carbon tetrachloride, or toluene. The uncertainty of the reported data is estimated to be within 310-11 m2s-1. To compute the thermodynamic correction factor an excess Gibbs energy model is required. Therefore, the applicability of COSMOSPACE to binary VLE predictions is thoroughly investigated. For this purpose a new method is developed to determine the required molecular parameters such as segment types, areas, volumes, and interaction parameters. So-called sigma profiles form the basis of this approach which describe the screening charge densities appearing on a molecule’s surface. To improve the prediction results a constrained two-parameter fitting strategy is also developed. These approaches are crucial to guarantee the physical significance of the segment parameters. Finally, the prediction quality of this approach is compared to the findings of the Wilson model, UNIQUAC, and the a priori predictive method COSMO-RS for a broad range of thermodynamic situations. The results show that COSMOSPACE yields results of similar quality compared to the Wilson model, while both perform much better than UNIQUAC and COSMO-RS. Since viscosity influences also the diffusion process, a new mixture viscosity model has been developed on the basis of Eyring’s absolute reaction rate theory. The nonidealities of the mixture are accounted for with the thermodynamically consistent COSMOSPACE approach. The required model and component parameters are derived from sigma-profiles, which form the basis of the a priori predictive method COSMO-RS. To improve the model performance two segment parameters are determined from a least-squares analysis to experimental viscosity data, whereas a constraint optimisation procedure is applied. In this way the parameters retain their physical meaning. Finally, the viscosity calculations of this approach are compared to the findings of the Eyring-UNIQUAC model for a broad range of chemical mixtures. These results show that the new Eyring-COSMOSPACE approach is superior to the frequently employed Eyring-UNIQUAC method. Finally, on the basis of Eyring’s absolute reaction rate theory a new model for the Maxwell-Stefan diffusivity has been developed. This model, an extension of the Vignes equation, describes the concentration dependence of the diffusion coefficient in terms of the diffusivities at infinite dilution and an additional excess Gibbs energy contribution. This energy part allows the explicit consideration of thermodynamic nonidealities within the modelling of this transport property. If the same set of interaction parameters, which has been derived from VLE data, is applied for this part and for the thermodynamic correction, a theoretically sound modelling of VLE and diffusion can be achieved. The influence of viscosity and thermodynamics on the model accuracy is thoroughly investigated. For this purpose diffusivities of 85 binary mixtures consisting of alkanes, cycloalkanes, halogenated alkanes, aromatics, ketones, and alcohols are computed. The average relative deviation between experimental data and computed values is approximately 8 % depending on the choice of the gE-model. These results indicate that this model is superior to some widely used methods. In summary, it can be said that the new approach facilitates the prediction of diffusion coefficients. The final equation is mathematically simple, universally applicable, and the prediction quality is as good as other models recently developed without having to worry about additional parameters, like pure component physical property data, self diffusion coefficients, or mixture viscosities. In contrast to many other models, the influence of the mixture viscosity can be omitted. Though a viscosity model is not required in the prediction of diffusion coefficients with the new equation, the models presented in this work allow a consistent modelling approach of diffusion, viscosity, and thermodynamics in liquid systems.

The aim of the thesis is the numerical investigation of saturated, stationary, incompressible Newtonian flow in porous media when inertia is not negligible. We focus our attention to the Navier-Stokes system with two pressures derived by two-scale homogenization. The thesis is subdivided into five Chapters. After the introductory remarks on porous media, filtration laws and upscaling methods, the first chapter is closed by stating the basic terminology and mathematical fundamentals. In Chapter 2, we start by formulating the Navier-Stokes equations on a periodic porous medium. By two-scale expansions of the velocity and pressure, we formally derive the Navier-Stokes system with two pressures. For the sake of completeness, known existence and uniqueness results are repeated and a convergence proof is given. Finally, we consider Stokes and Navier-Stokes systems with two pressures with respect to their relation to Darcy's law. Chapter 3 and Chapter 4 are devoted to the numerical solution of the nonlinear two pressure system. Therefore, we follow two approaches. The first approach which is developed in Chapter 3 is based on a splitting of the Navier-Stokes system with two pressures into micro and macro problems. The splitting is achieved by Taylor expanding the permeability function or by discretely computing the permeability function. The problems to be solved are a series of Stokes and Navier-Stokes problems on the periodicity cell. The Stokes problems are solved by an Uzawa conjugate gradient method. The Navier-Stokes equations are linearized by a least-squares conjugate gradient method, which leads to the solution of a sequence of Stokes problems. The macro problem consists of solving a nonlinear uniformly elliptic equation of second order. The least-squares linearization is applied to the macro problem leading to a sequence of Poisson problems. All equations will be discretized by finite elements. Numerical results are presented at the end of Chapter 3. The second approach presented in Chapter 4 relies on the variational formulation in a certain Hilbert space setting of the Navier-Stokes system with two pressures. The nonlinear problem is again linearized by the least-squares conjugate gradient method. We obtain a sequence of Stokes systems with two pressures. For the latter systems, we propose a fast solution method which relies on pre-computing Stokes systems on the periodicity cell for finite element basis functions acting as right hand sides. Finally, numerical results are discussed. In Chapter 5 we are concerned with modeling and simulation of the pressing section of a paper machine. We state a two-dimensional model of a press nip which takes into account elasticity and flow phenomena. Nonlinear filtration laws are incorporated into the flow model. We present a numerical solution algorithm and the chapter is closed by a numerical investigation of the model with special focus on inertia effects.

Sterisch anspruchsvolle Cyclopentadienyl-Liganden wurden zur Stabilisierung neuer Mono(cyclopentadienyl) Verbindungen der schweren Erdalkalimetalle eingesetzt und deren Funktionalisierbarkeit dieser Spezies wurde exemplarisch durch die Synthese neutraler Tripeldecker-Sandwichkomplexe demonstriert. Die dabei ausgebildeten Molekülstrukturen lassen sich mittels DFT-Rechnungen zuverlässig vorhersagen. In diesem Zusammenhang wurde ebenfalls der Cyclononatetraenyl-Ligand, dessen Komplexeigenschaften bisher nur unzureichend untersucht wurden, eingesetzt. Im Rahmen dieser Arbeit gelang die Synthese des Bis(cyclononatetraenyl)bariums, Ba(C9H9)2, und dessen spektroskopische Charakterisierung. DFT-Rechnungen sagen für diesen Komplex eine Metallocenstruktur mit nahezu parallelen Ringen und einem Ba-Ring Abstand von 2.37 Å voraus. Durch den Einsatz des Tetraisopropylcyclopentadienyl (4Cp) und Tri(tert.-butyl)cyclopentadienyl (Cp’)-Liganden gelang die Synthese von Bis- und Monocyclopentadienyl-Verbindungen der frühen und späten Lanthanoide. Besonders interessant in diesem Zusammenhang ist die erfolgreiche Darstellung des Azido-Clusters, [Na(dme)3]2[4Cp6Yb6(N3)14] (4Cp= (Me2CH)4C5H), der die unterschiedlichen Koordinationsmöglichkeiten des Azido-Liganden in einem einzigen Komplex vereint. Vergleichbare Komplexe waren in der Organolanthanoidchemie bisher unbekannt. Durch Substitution am Cyclopentadienyl-System lassen sich dessen elektronische und sterische Eigenschaften signifikant verändern. Die Auswirkungen dieser Effekte können sehr eindrucksvoll an Manganocen-Komplexen demonstriert werden, in denen sich der low- und high-spin Zustand energetisch nur sehr wenig unterscheiden. Der elektronische Grundzustand einer Reihe unterschiedlich substituierter Manganocen-Komplexe wurde mittels Festkörpermagnetismus, ESR, Röntgenstrukturanalyse, EXAFS und variabler Temperatur UV-Vis Spektroskopie bestimmt, und mit dem Substitutionsmuster am Cyclopentadienyl-System korreliert. Spin-Gleichgewichte ließen sich für [(Me3C)C5H4]2Mn, [(Me3C)2C5H3]2Mn und [(Me3C)(Me3Si)C5H3]2Mn nachweisen. Theoretische Rechnungen postulieren, dass Cerocen, Ce(C8H8)2, ein Beispiel für Moleküle mit gemischt-konfiguriertem Grundzustand sei, der durch 80 % [(Ce)f1e2u(cot)e2u3] und 20 % [(Ce)f0e2u(cot)e2u4] beschreiben werden könne. Obwohl dieses Molekül bereits seit 1976 bekannt ist, ist dessen elektronische Struktur bis heute sehr umstritten. Im Rahmen dieser Arbeit wurden neue Synthesekonzepte für diese Verbindung entwickelt und die elektronische Struktur mittels magnetischer Messungen im Festkörper, EXAFS und XANES Studien untersucht. Die dabei erhaltenen Daten sind in sehr guter Übereinstimmung mit den theoretischen Rechnungen und belegen die Bedeutung eines gemischt-konfigurierten Grundzustandes bei der Bindung in Organometallkomplexen der f-Block Metalle. Während in Cerocen nur ein temperaturunabhängiger Paramagnetismus (TIP) beobachtet werden kann, findet man eine starke Temperaturabhängigkeit der magnetischen Suszeptibilität in Ytterbium Systemen des Typs Cp’2Yb(bipy’) [Cp´ und bipy´ sind substituierte Cyclopentadienyl- oder 4,4’-substituierter 2,2’-Bipyridyl-Liganden]. Temperaturabhängige XANES-Experimenten belegen, dass auch in diesen Systemen ein gemischt-konfigurierter Grundzustand vorliegt, der durch [(Yb)f14(bipy)b1()0] und [(Yb)f13(bipy)b1()1] beschreiben werden kann. Der relative Anteil beider Wellenfunktionen zum Grundzustand wird durch Substitution am 2,2’-Bipyridyl- oder Cyclopentadienyl-System signifikant beeinflusst. Modelle, mit denen sich dieses Verhalten qualitativ beschreiben lässt, wurden im Rahmen dieser Arbeit entwickelt. Ein kinetisch stabilisiertes, adduktfreies Titanocen wurde unter Verwendung des Di(tert.-butyl)cyclopentadienyl Liganden hergestellt und dessen Reaktivität gegenüber kleinen Molekülen, z.B. CO, N2 und H2 untersucht. Im Rahmen der Reaktivitätsstudien wurden ebenfalls 2,2’-Bipyridyl Addukte an das Cp’2Ti Fragment synthetisiert und deren magnetische Eigenschaften erforscht. Durch Variationen am 2,2’-Bipyridyl System lässt sich das Singlet-Triplet Splitting in diesem System gezielt steuern.