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Nanoparticle-Filled Thermoplastics and Thermoplastic Elastomer: Structure-Property Relationships
(2012)

The present work focuses on the structure-property relationships of
particulate-filled thermoplastics and thermoplastic elastomer (TPE). In this work
two thermoplastics and one TPE were used as polymer matrices, i.e. amorphous
bisphenol-A polycarbonate (PC), semi-crystalline isotactic polypropylene (iPP),
and a block copolymer poly(butylene terephthalate)-block-poly(tetramethylene
glycol) TPE(PBT-PTMG). For PC, a selected type of various Aerosil® nano-SiO2
types was used as filler to improve the thermal and mechanical properties by
maintaining the transparency of PC matrix. Different types of SiO2 and TiO2
nanoparticles with different surface polarity were used for iPP. The goal was to
examine the influence of surface polarity and chemical nature of nanoparticles on
the thermal, mechanical and morphological properties of iPP composites. For
TPE(PBT-PTMG), three TiO2 particles were used, i.e. one grade with hydroxyl
groups on the particle surface and the other two grades are surface-modified with
metal and metal oxides, respectively. The influence of primary size and dispersion
quality of TiO2 particles on the properties of TPE(PBT-PTMG)/TiO2 composites
were determined and discussed.
All polymer composites were produced by direct melt blending in a twin-screw
extruder via masterbatch technique. The dispersion of particles was examined by
using scanning electron microscopy (SEM) and micro-computerized tomography
(μCT). The thermal and crystalline properties of polymer composites were characterized by using thermogravimetric analysis (TGA) and differential
scanning calorimetry (DSC). The mechanical and thermomechanical properties
were determined by using mechanical tensile testing, compact tension and
Charpy impact as well as dynamic-mechanical thermal analysis (DMTA).
The SEM results show that the unpolar-surface modified nanoparticles are better
dispersed in polymer matrices as iPP than polar-surface nanoparticles, especially
in case of using Aeroxide® TiO2 nanoparticles. The Aeroxide® TiO2 nanoparticles
with a polar surface due to Ti-OH groups result in a very high degree of
agglomeration in both iPP and TPE matrices because of strong van der Waals
interactions among particles (hydrogen bonding). Compared to unmodified
Aeroxide® TiO2 nanoparticles, the other grades of surface modified TiO2 particles
are very homogenously dispersed in used iPP and TPE(PBT-PTMG). The
incorporation of SiO2 nanoparticles into bisphenol-A PC significantly increases
the mechanical properties of PC/SiO2 nanocomposites, particularly the resistance
against environmental stress crazing (ESC). However, the transparency of
PC/SiO2 nanocomposites decreases with increasing nanoparticle content and
size due to a mismatch of infractive indices of PC and SiO2 particles. The different
surface polarity of nanoparticles in iPP shows evident influence on properties of
iPP composites. Among iPP/SiO2 nanocomposites, the nanocomposite
containing SiO2 nanoparticles with a higher degree of hydrophobicity shows
improved fracture and impact toughness compared to the other iPP/SiO2
composites. The TPE(PBT-PTMG)/TiO2 composites show much better thermal and mechanical properties than neat TPE(PBT-PTMG) due to strong chemical
interactions between polymer matrix and TiO2 particles. In addition, better
dispersion quality of TiO2 particles in used TPE(PBT-PTMG) leads to dramatically
improved mechanical properties of TPE(PBT-PTMG)/TiO2 composites.

Induction welding is a technique for joining of thermoplastic composites. An alternating
electromagnetic field is used for contact-free and fast heating of the parts to be
welded. In case of a suitable reinforcement structure heat generation occurs directly
in the laminate with complete heating in thickness direction in the vicinity of the coil.
The resulting temperature field is influenced by the distance to the induction coil with
decreasing temperature for increasing distance. Consequently, the surface facing the
inductor yields the highest, the opposite surface the lowest temperature.
The temperature field described significantly complicates the welding process. Due to
complete heating the laminate has to be loaded with pressure in order to prevent delamination,
which requires the usage of complex and expensive welding tools. Additionally,
the temperature difference between the inductor and the opposite side may
be greater than the processing window, which is determined by the properties of the
matrix polymer.
The induction welding process is influenced by numerous parameters. Due to complexity
process development is mainly based on experimental studies. The investigation
of parameter influences and interactions is cumbersome and the measurement
of quality relevant parameters, especially in the bondline, is difficult. Process simulation
can reduce the effort of parameter studies and contribute to further analysis of
the induction welding process.
The objective of this work is the development of a process variant of induction welding
preventing complete heating of the laminate in thickness direction. For optimal
welding the bondline has to reach the welding temperature whereas the other domains
should remain below the melting temperature of the matrix polymer.
For control of the temperature distribution localized cooling by an impinging jet of
compressed air was implemented. The effect was assessed by static heating experiments
with carbon fiber reinforced polyetheretherketone (CF/PEEK) and polyphenylenesulfide
(CF/PPS).
The application of localized cooling could influence the temperature distribution in
thickness direction of the laminate, according to the specifications of the welding
process. The temperature maximum was shifted from the inductor to the opposite side. This enables heating of the laminate to welding temperature in the bondline and
concurrently preventing melting and effects connected to this on the outer surface.
Inductive heating and the process variant with localized cooling were implemented in
three-dimensional finite-element process models. For that purpose, the finiteelement-
software Comsol Multiphysics 4.1 was used for the development of fully
coupled electromagnetic-thermal models which have been validated experimentally.
A sensitivity analysis for determination of different processing parameters of inductive
heating was conducted. The coil current, field frequency, and heat capacity were
identified as significant parameters. The cooling effect of the impinging jets was estimated
by appropriate convection coefficients.
For transfer of the developed process variant to the continuous induction welding
process, a process model was created. It represents a single overlap joint with continuous
feed. With the help of process modeling a parameter set for welding of
CF/PEEK was determined and used for joining of specimens. In doing so, the desired
temperature field was achieved and melting of the outer layers could be prevented.

Unidirectional (UD) composites are the most competitive materials for the production
of high-end structures. Their field of application spreads from the aerospace up to
automotive and general industry sector. Typical examples of components made of
unidirectional reinforced composite materials are rocket motor cases, drive shafts or
pressure vessels for hydrogen storage. The filament winding technology, the pultrusion
process and the tape placement are processes suitable for the manufacturing
using UD semi-finished products. The demand for parts made of UD composites is
constantly increasing over the last years. A key feature for the success of this technology
is the improvement of the manufacturing procedure.
Impregnation is one of the most important steps in the manufacturing process. During
this step the dry continuous fibers are combined with the liquid matrix in order to create
a fully impregnated semi-finished product. The properties of the impregnated roving
have a major effect on the laminate quality, and the efficient processing of the
liquid matrix has a big influence on the manufacturing costs.
The present work is related to the development of a new method for the impregnation
of carbon fiber rovings with thermoset resin. The developed impregnation unit consists
of a sinusoidal cavity without any moving parts. The unit in combination with an
automated resin mixing-dosing system allows complete wet-out of the fibers, precise
calibration of the resin fraction, and stable processing conditions.
The thesis focuses on the modeling of the impregnation process. Mathematical expressions
for the fiber compaction, the gradual increase of the roving tension, the
static pressure, the capillarity inside the filaments of the roving, and the fiber permeation
are presented, discussed, and experimentally verified. These expressions were
implemented in a modeling algorithm. The model takes into account all the relevant
material and process parameters. An experimental set-up based on the filament
winding process was used for the validation of the model. Trials under different conditions
have been performed. The results proved that the model can accurately simulate
the impregnation process. The good impregnation degree of the wound samples
confirmed the efficiency of the developed impregnation unit. A techno economical
analysis has proved that the developed system will result to the reduction of the
manufacturing costs and to the increase of the productivity.

Thermoplastic polymer-polymer composites consist of a polymeric matrix and a
polymeric reinforcement. The combination of these materials offers outstanding
mechanical properties at lower weight than standard fiber reinforced materials.
Furthermore, when both polymeric components originate from the same family or,
ideally, from the same polymer, their sustainability degree is higher than standard
fiber reinforced composites.
A challenge of polymer-polymer composites is the subsequent processing of their
semi-finished materials by heating techniques. Since the fibers are made of meltable
thermoplastic, the reinforcing fiber structure might be lost during the heating process.
Hence, the mechanical properties of an overheated polymer-polymer composite
would decline, and finally, they would be even lower than the neat matrix. A decrease
of process temperature to manage the heating challenge is not reasonable since the
cycle time would be increased at the same time. Therefore, this work pursues the
adaption of a fast and selective heating method on the use with polymer-polymer
composites. Inductively activatable particles, so-called susceptors, were distributed in
the matrix to evoke a local heating in the matrix when being exposed to an
alternating magnetic field. In this way, the energy input to the fibers is limited.
The experimental series revealed the induction particle heating effect to be mainly
related to susceptor material, susceptor fraction, susceptor distribution as well as
magnetic field strength, coupling distance, and heating time. A proper heating was
achieved with ferromagnetic particles at a filler content of only 5 wt-% in HDPE as
well as with its respective polymer fiber reinforced composites. The study included
the analysis of susceptor impact on mechanical and thermal matrix properties as well
as a degradation evaluation. The susceptors were identified to have only a marginal
impact on matrix properties. Furthermore, a semi-empiric simulation of the particle
induction heating was applied, which served for the investigation of intrinsic melting
processes.
The achieved results, the experimental as well as the analytic study, were
successfully adapted to a thermoforming process with a polymer-polymer material,
which had been preheated by means of particle induction.

An isogeometric Reissner-Mindlin shell derived from the continuum theory is presented. The geometry is described by NURBS surfaces. The kinematic description of the employed shell theory requires the interpolation of the director vector and of a local basis system. Hence, the definition of nodal basis systems at the control points is necessary for the proposed formulation. The control points are in general not located on the shell reference surface and thus, several choices for the nodal values are possible. The proposed new method uses the higher continuity of the geometrical description to calculate nodal basis system and director vectors which lead to geometrical exact interpolated values thereof. Thus, the initial director vector coincides with the normal vector even for the coarsest mesh. In addition to that a more accurate interpolation of the current director and its variation is proposed. Instead of the interpolation of nodal director vectors the new approach interpolates nodal rotations. Account is taken for the discrepancy between interpolated basis systems and the individual nodal basis systems with an additional transformation. The exact evaluation of the initial director vector along with the interpolation of the nodal rotations lead to a shell formulation which yields precise results even for coarse meshes. The convergence behavior is shown to be correct for k-refinement allowing the use of coarse meshes with high orders of NURBS basis functions. This is potentially advantageous for applications with high numerical effort per integration point. The geometrically nonlinear formulation accounts for large rotations. The consistent tangent matrix is derived. Various standard benchmark examples show the superior accuracy of the presented shell formulation. A new benchmark designed to test the convergence behavior for free form surfaces is presented. Despite the higher numerical effort per integration point the improved accuracy yields considerable savings in computation cost for a predefined error bound.

The development of autonomous vehicle systems demands the increased usage of software based control mechanisms. Generally, this leads to very complex systems, whose proper functioning has to be ensured. In our work we aim at investigating and assessing the potential effects of software issues on the safety, reliability and availability of complex embedded autonomous systems. One of the key aspects of the research concerns the mapping of functional descriptions in form of integrated behavior-based control networks to State-Event Fault Tree models.

Recently, a new Quicksort variant due to Yaroslavskiy was chosen as standard sorting
method for Oracle's Java 7 runtime library. The decision for the change was based on
empirical studies showing that on average, the new algorithm is faster than the formerly
used classic Quicksort. Surprisingly, the improvement was achieved by using a dual pivot
approach — an idea that was considered not promising by several theoretical studies in the
past. In this thesis, I try to find the reason for this unexpected success.
My focus is on the precise and detailed average case analysis, aiming at the flavor of
Knuth's series “The Art of Computer Programming”. In particular, I go beyond abstract
measures like counting key comparisons, and try to understand the efficiency of the
algorithms at different levels of abstraction. Whenever possible, precise expected values are
preferred to asymptotic approximations. This rigor ensures that (a) the sorting methods
discussed here are actually usable in practice and (b) that the analysis results contribute to
a sound comparison of the Quicksort variants.

Capital budgeting or investment decisions have an essential influence on companies’ performance. Instead of a rational choice, capital budgeting might be regarded as a process of reality construction. Research suggests that decision makers have only limited control over their own cognitive biases in this construction process. It is in this perspective that this paper intends to answer the following research question: What are behavioral determinants for a successful capital-budgeting decision process? The authors identify and discuss three behavioral success factors (reflective prudence, critical communication and outcome independence) for five stages of the capital budgeting process against the backdrop of the findings of the managerial and organizational cognition theory and cognitive psychology.

In this study, two outstanding subgroups of organic-inorganic hybrid materials have been investigated. The first part covers the design, synthesis, characterization and application of seven novel Metal Organic Frameworks (MOFs) containing functionalized biphenyl dicarboxylates as linkers. In the second part, the surface modification of the metal oxides ZrO2, TiO2 and Al2O3 using phosphonate derivates is reported.
Firstly three functionalized MOF structures; ZnBrBPDC, ZnNO2BPDC and ZnNH2BPDC were synthesised using 4,4´-biphenyldicarboxylic acid derivatives with different functional groups (-Br, -NO2, -NH2) Powder X-ray diffraction (PXRD) measurements indicated that the synthesised MOFs posses the interpenetrated IRMOF-9 structure with a cubic topology, which was also confirmed with single crystal X-ray measurements. The chemical structure of the MOF materials was further proved by solid state NMR and IR measurements. N2 adsorption measurements showed Type I isotherms for all three structures with large surface areas. TGA measurements of the evacuated samples were in good agreement with the elemental analysis data. The results proved that their thermal stability is between 325 °C - 450 °C.
Adsorption properties of these MOF structures were tested using light alkanes (CH4, C2H6, C3H8, and n-C4H10) at three different temperatures. For all adsorbents, the maximum uptakes were observed at 273 K. When the temperature was increased, the amount of the adsorbed gas decreased. All three MOFs showed strong affinities for n-butane. The lowest uptakes were observed for CH4.
The effect of functional groups on the IRMOF series was also examined by synthesizing amide functionalized biphenyl linkers. For this purpose, four different linkers containing amides with different alkyl chains (C1-C4) were synthesized and used for the synthesis of four new MOF structures ZnAcBPDC, ZnPrBPDC, ZnBuBPDC and ZnPeBPDC.
PXRD measurements of ZnAcBPDC indicated that the structure contains two different phases. PXRD patterns of ZnPrBPDC, ZnBuBPDC and ZnPeBPDC revealed non-interpenetrated structures which were further proved by single crystal X-ray measurements. The chemical structure of the MOF materials was further confirmed by X-ray spectoscopy, solid state NMR and IR measurements.
N2 adsorption measurements of the MOF structures were carried out using different activation methods. For all four MOFs, Type I isotherms were obtained. ZnAcBPDC showed the highest BET surface area. ZnAcBPDC and ZnBuBPDC were tested for their alkane, alkene and CO2 adsorption capacities.
In the second part of the work, the surface modification of three different metal oxides, ZrO2, TiO2 and Al2O3 was performed. For this purpose firstly three different fluorescent phosphonate derivatives containing thiophene units were synthesized from their halo derivatives in a four step synthesis and then used as coupling molecules for the surface modification. Nine different surfaces were obtained (38@TiO2, 39@TiO2, 40@TiO2, 38@Al2O3, 39@Al2O3, 40@Al2O3, 38@ZrO2, 39@ZrO2, 40@ZrO2).
All three modified metal oxide surfaces were characterized using elemental analysis, solid state NMR and IR spectroscopy. The BET surface areas of the materials were determined by N2 adsorption measurements. TGA was used to determine the stability of the surfaces. Maximum loadings were obtained for ZrO2 surfaces.
Due to the strong luminescence of the coupling molecules, the modified surfaces were checked for their light emission. All ZrO2 and Al2O3 surfaces showed fluorescence with exception of 40@Al2O3. On the other hand, for the modified TiO2 surfaces, no fluorescence could be observed.

By natural or man-made disasters, the evacuation of a whole region or city may become necessary. Apart from private traffic, the evacuation from collection points to secure shelters outside the endangered region will be realized by a bus fleet made available by emergency relief. The arising Bus Evacuation Problem (BEP) is a vehicle scheduling problem, in which a given number of evacuees needs to be transported from a set of collection points to a set of capacitated shelters, minimizing the total evacuation time, i.e., the time needed until the last person is brought to safety.
In this paper we consider an extended version of the BEP, the Robust Bus Evacuation Problem (RBEP), in which the exact numbers of evacuees are not known, but may stem from a set of probable scenarios. However, after a given reckoning time, this uncertainty is eliminated and planners are given exact figures. The problem is to decide for each bus, if it is better to send it right away -- using uncertain numbers of evacuees -- or to wait until the numbers become known.
We present a mixed-integer linear programming formulation for the RBEP and discuss solution approaches; in particular, we present a tabu search framework for finding heuristic solutions of acceptable quality within short computation time. In computational experiments using both randomly generated instances and the real-world scenario of evacuating the city of Kaiserslautern, we compare our solution approaches.

I report on two experiments, which were designed to test theoretical predictions about individual behavior in a duopolistic setting. With quantity being the choice variable a simultaneous Cournot game and a sequential Stackelberg game were tested over two periods. The key feature of both models was that players were able to lower marginal cost for period two if they successfully outperformed their competition in period one in terms of profit. Experimental results suggest that in the Cournot game players are very competitive in period one but become Cournot players in period two. In the Stackelberg game Cournot play is modal, suggesting that players have preferences for equality in payoffs, which maybe brought about by punishment of Stackelberg followers and fear of punishment of Stackelberg leaders . Overall, players earned more money in the Stackelberg game than in the Cournot game.

Generic layout analysis--process of decomposing document image into homogeneous regions for a collection of diverse document images--has many important applications in document image analysis and understanding such as preprocessing of degraded warped, camera-captured document images, high performance layout analysis of document images containing complex cursive scripts, and word spotting in historical document images at page level. Many areas in this field like generic text line extraction method are considered as elusive goals so far, still beyond the reach of the state-of-the-art methods [NJ07, LSZT07, KB06]. This thesis addresses this problem in such a way that it presents generic, domain-independent, text line extraction and text and non-text segmentation methods, and then describes some important applications, that were developed based on these methods. An overview of the key contributions of this thesis is as follows.
The first part of this thesis presents a generic text line extraction method using a combination of matched filtering and ridge detection techniques, which are commonly used in computer vision. Unlike the state-of-the-art text line extraction methods in the literature, the generic text line extraction method can be equally and robustly applied to a large variety of document image classes including scanned and camera-captured documents, binary and grayscale documents, typed-text and handwritten documents, historical and contemporary documents, and documents containing different scripts. Different standard datasets are selected for performance evaluation that belong to different categories of document images such as the UW-III [GHHP97] dataset of scanned documents, the ICDAR 2007 [GAS07] and the UMD [LZDJ08] datasets of handwritten documents, the DFKI-I [SB07] dataset of camera-captured documents, Arabic/Urdu script documents dataset, and German calligraphic (Fraktur) script historical documents dataset. The generic text line extraction method achieves 86% (n = 23,763 text lines in 650 documents) text line detection accuracy which is better than the aggregate accuracy of 73% of the best performing domain-specific state-of-the-art methods. To the best of the author's knowledge, it is the first general-purpose text line extraction method that can be equally used for a diverse collection of documents.
This thesis also presents an active contour (snake) based curled text line extraction method for warped, camera-captured document images. The presented approach is applied to DFKI-I [SB07] dataset of camera-captured, Latin script document images for curled text line extraction. It achieves above 95% (n = 3,091 text lines in 102 documents) text line detection accuracy, which is significantly better than the competing state-of-the-art curled text line extraction methods. The presented text line extraction method can also be applied to document images containing different scripts like Chinese, Devanagari, and Arabic after small modifications.
The second part of this thesis presents an improved version of the state-of-the-art multiresolution morphology (Leptonica) based text and non-text segmentation method [Blo91], which is a domain-independent page segmentation approach and can be equally applied to a diverse collection of binarized document images. It is demonstrated that the presented improvements result in an increase in segmentation accuracy from 93% to 99% (n = 113 documents).
This thesis also introduces a discriminative learning based approach for page segmentation, where a self-tunable multi-layer perceptron (MLP) classifier [BS10] is trained for distinguishing between text and non-text connected components. Unlike other classification based page segmentation approaches in the literature, the connected components based discriminative learning based approach is faster than pixel based classification methods and does not require a block segmentation method beforehand. A segmentation accuracy of $96\%$ ($n = 113$ documents) is achieved in comparison to the state-of-the-art multiresolution morphology (Leptonica) based page segmentation method [Blo91] that achieves a segmentation accuracy of 93%. In addition to text and non-text segmentation of Latin script documents, the presented approach can also be adapted for document images containing other scripts as well as for other specialized layout analysis tasks such as digit and non-digit segmentation [HBSB12], orientation detection [RBSB09], and body-text and side-note segmentation [BAESB12].
Finally, this thesis presents important applications of the two generic layout analysis techniques, ridge-based text line extraction method and the multi-resolution morphology based text and non-text segmentation method, discussed above. First, a complete preprocessing pipeline is described for removing different types of degradations from grayscale warped, camera-captured document images that includes removal of grayscale degradations such as non-uniform shadows and blurring through binarization, noise cleanup applying page frame detection, and document rectification using monocular dewarping. Each of these preprocessing steps shows significant improvement in comparison to the analyzed state-of-the-art methods in the literature. Second, a high performance layout analysis method is described for complex Arabic script document images written in different languages such as Arabic, Urdu, and Persian and different styles for example Naskh and Nastaliq. The presented layout analysis system is robust against different types of document image degradations and shows better performance for text and non-text segmentation, text line extraction, and reading order determination on a variety of Arabic and Urdu document images as compared to the state-of-the-art methods. It can be used for large scale Arabic and Urdu documents' digitization processes. These applications demonstrate that the layout analysis methods, ridge-based text line extraction and the multi-resolution morphology based text and non-text segmentation, are generic and can be applied easily to a large collection of diverse document images.

This research for this thesis was conducted to develop a framework which supports the automatic configuration of project-specific software development processes by selecting and combining different technologies: the Process Configuration Framework. The research draws attention to the problem that while the research community develops new technologies, the industrial companies continue only using their well-known ones. Because of this, technology transfer takes decades. In addition, there is the fact that there is no solution which solves all problems in a software development project. This leads to a number of technologies which need to be combined for one project.
The framework developed and explained in this research mainly addresses those problems by building a bridge between research and industry as well as by supporting software companies during the selection of the most appropriate technologies combined in a software process. The technology transformation gap is filled by a repository of (new) technologies which are used as a foundation of the Process Configuration Framework. The process is configured by providing SPEM process pattern for each technology, so that the companies can build their process by plugging into each other.
The technologies of the repository were specified in a schema including a technology model, context model, and an impact model. With context and impact it is possible to provide information about a technology, for example, its benefits to quality, cost or schedule. The offering of the process pattern as output of the Process Configuration Framework is performed in several stages:
I Technology Ranking:
1 Ranking based on Application Domain, Project & Impact
2 Ranking based on Environment
3 Ranking based on Static Context
II Technology Combination:
4 Creation of all possible Technology Chains
5 Restriction of the Technology Chains
6 Ranking based on Static and Dynamic Context
7 Extension of the Chains by Quality Assurance
III Process Configuration:
8 Process Component Diagram
9 Extension of the Process Component Diagram
10 Instantiation of the Components by Technologies of the Technology Chain
11 Providing process patterns
12 Creation of the process based on Patterns
The effectiveness and quality of the Process Configuration Framework have additionally been evaluated in a case study. Here, the Technology Chains manually created by experts were compared to the chains automatically created by the framework after it was configured by those experts. This comparison depicted that the framework results are similar and therefore can be used as a recommendation.
We conclude from our research that support during the configuration of a process for software projects is important especially for non-experts. This support is provided by the Process Configuration Framework developed in this research. In addition our research has shown that this framework offers a possibility to speed up the technology transformation gap between the research community and industrial companies.

Wechselnde Umweltbedingungen wie Temperaturveränderungen oder der Zugang zu Nährstoffen erfordern spezielle genetische Anpassungsprogramme, vor allem von sessilen Organismen wie Pflanzen. Ein solcher hochkonservierter Mechanismus, der unter anderem vor Temperaturspitzen schützt, ist die von Hitzeschockfaktoren (HSF) kontrollierte Hitzeschockantwort (HSR). Dabei werden vermehrt spezifische Hitzestressproteine (HSPs, Chaperone) gebildet, die Proteine vor Denaturierung schützen. In Pflanzen hat sich ein hochkomplexes regulatorisches Netzwerk gebildet, das aus über 20 HSFs besteht, das eine genaue Feinabstimmung der HSR auf die jeweiligen Stressbedingungen erlaubt.
Das hohe Maß an Komplexität der HSR in Pflanzen erschwert die wissenschaftliche Zugänglichkeit jedoch erheblich. Um die grundlegenden Prinzipien der HSR in Pflanzen zu verstehen griffen wir deshalb auf einen einfacheren Modellorganismus zurück, der Pflanzen sehr nahe steht aber nur einen einzigen HSF (HSF1) enthält, der einzelligen Grünalge Chlamydomonas reinhardtii. Im Rahmen dieser Arbeit wurden dazu drei Ansätze verfolgt.
Als erstes wurden verschiedene chemische Substanzen eingesetzt die unterschiedliche Schritte während der Aktivierung und Abschaltung der HSR hemmen um darüber die Regulation der HSR aufzuklären. Dabei wurde festgestellt, dass die Phosphorylierung von HSF1 eine entscheidende Rolle in der Aktivierung der HSR spielt, das auslösende Momentum die Anhäufung von falsch gefalteten Proteinen ist und das HSP90A aus dem Cytosol eine wichtige modulierende Rolle bei der HSR spielt.
Als zweites wurde die Veränderung sämtlicher Transkripte mithilfe von Microarrays gemessen, um vor allem pflanzenspezifische Prozesse zu identifizieren, die auf erhöhte Temperaturen gezielt angepasst werden müssen. Dabei konnte die Chlorophyll Biosynthese und der Transport von Proteinen in den Chloroplasten als neue, pflanzenspezifische Ziele der Stressantwort identifiziert werden. Des Weiteren konnte direkt gezeigt werden, das HSF1 auch plastidäre Chaperone reguliert, im Gegensatz zu mitochondrialen Chaperonen die getrennt gesteuert werden.
Als letztes wurde gezielt die Expression wichtiger Gene für die Stressantwort (HSF1/HSP70B) unterdrückt, um den Einfluss dieser Gene auf die HSR genauer zu studieren. Dazu habe ich ein in der einzelligen Grünalge neuartiges System entwickelt, basierend auf dem RNAi Mechanismus, dass es erlaubt abhängig von der Stickstoffquelle im Nährmedium auch essentielle Gene gezielt auszuschalten. Dieses System erlaubte es zu zeigen, dass HSF1 selbst während des Stresses die Expression seiner RNA erhöht, und dies gezielt tut um die Stressantwort weiter zu verstärken. Es konnte weiter gezeigt werden, dass das Chloroplasten Chaperon HSP70B ein essentielles Protein für das Zellwachstum ist, welches mithilfe des induzierbaren RNAi Systems genauer untersucht werden kann. Dabei wurde festgestellt, dass die HSP70B vermittelte Assemblierung und Disassemblierung des VIPP1 Proteins entscheidend ist für dessen Funktion in der Zelle. Des Weiteren konnte gezeigt werde, dass HSP70B wahrscheinlich verantwortlich ist für die Faltung eines oder mehrerer noch unbekannter Enzyme der Arginin Biosynthese oder der Stickstofffixierung, und das diese Prozesse wahrscheinlich die essentielle Funktion von HSP70B darstellen.

The main topic of this thesis is to define and analyze a multilevel Monte Carlo algorithm for path-dependent functionals of the solution of a stochastic differential equation (SDE) which is driven by a square integrable, \(d_X\)-dimensional Lévy process \(X\). We work with standard Lipschitz assumptions and denote by \(Y=(Y_t)_{t\in[0,1]}\) the \(d_Y\)-dimensional strong solution of the SDE.
We investigate the computation of expectations \(S(f) = \mathrm{E}[f(Y)]\) using randomized algorithms \(\widehat S\). Thereby, we are interested in the relation of the error and the computational cost of \(\widehat S\), where \(f:D[0,1] \to \mathbb{R}\) ranges in the class \(F\) of measurable functionals on the space of càdlàg functions on \([0,1]\), that are Lipschitz continuous with respect to the supremum norm.
We consider as error \(e(\widehat S)\) the worst case of the root mean square error over the class of functionals \(F\). The computational cost of an algorithm \(\widehat S\), denoted \(\mathrm{cost}(\widehat S)\), should represent the runtime of the algorithm on a computer. We work in the real number model of computation and further suppose that evaluations of \(f\) are possible for piecewise constant functions in time units according to its number of breakpoints.
We state strong error estimates for an approximate Euler scheme on a random time discretization. With this strong error estimates, the multilevel algorithm leads to upper bounds for the convergence order of the error with respect to the computational cost. The main results can be summarized in terms of the Blumenthal-Getoor index of the driving Lévy process, denoted by \(\beta\in[0,2]\). For \(\beta <1\) and no Brownian component present, we almost reach convergence order \(1/2\), which means, that there exists a sequence of multilevel algorithms \((\widehat S_n)_{n\in \mathbb{N}}\) with \(\mathrm{cost}(\widehat S_n) \leq n\) such that \( e(\widehat S_n) \precsim n^{-1/2}\). Here, by \( \precsim\), we denote a weak asymptotic upper bound, i.e. the inequality holds up to an unspecified positive constant. If \(X\) has a Brownian component, the order has an additional logarithmic term, in which case, we reach \( e(\widehat S_n) \precsim n^{-1/2} \, (\log(n))^{3/2}\).
For the special subclass of $Y$ being the Lévy process itself, we also provide a lower bound, which, up to a logarithmic term, recovers the order \(1/2\), i.e., neglecting logarithmic terms, the multilevel algorithm is order optimal for \( \beta <1\).
An empirical error analysis via numerical experiments matches the theoretical results and completes the analysis.

This thesis is devoted to furthering the tropical intersection theory as well as to applying the
developed theory to gain new insights about tropical moduli spaces.
We use piecewise polynomials to define tropical cocycles that generalise the notion of tropical Cartier divisors to higher codimensions, introduce an intersection product of cocycles with tropical cycles and use the connection to toric geometry to prove a Poincaré duality for certain cases. Our
main application of this Poincaré duality is the construction of intersection-theoretic fibres under a
large class of tropical morphisms.
We construct an intersection product of cycles on matroid varieties which are a natural
generalisation of tropicalisations of classical linear spaces and the local blocks of smooth tropical
varieties. The key ingredient is the ability to express a matroid variety contained in another matroid variety by a piecewise polynomial that is given in terms of the rank functions of the corresponding
matroids. In particular, this enables us to intersect cycles on the moduli spaces of n-marked abstract
rational curves. We also construct a pull-back of cycles along morphisms of smooth varieties, relate
pull-backs to tropical modifications and show that every cycle on a matroid variety is rationally
equivalent to its recession cycle and can be cut out by a cocycle.
Finally, we define families of smooth rational tropical curves over smooth varieties and construct a tropical fibre product in order to show that every morphism of a smooth variety to the moduli space of abstract rational tropical curves induces a family of curves over the domain of the morphism.
This leads to an alternative, inductive way of constructing moduli spaces of rational curves.

Recently convex optimization models were successfully applied
for solving various problems in image analysis and restoration.
In this paper, we are interested in relations between
convex constrained optimization problems
of the form
\({\rm argmin} \{ \Phi(x)\) subject to \(\Psi(x) \le \tau \}\)
and their penalized counterparts
\({\rm argmin} \{\Phi(x) + \lambda \Psi(x)\}\).
We recall general results on the topic by the help of an epigraphical projection.
Then we deal with the special setting \(\Psi := \| L \cdot\|\) with \(L \in \mathbb{R}^{m,n}\)
and \(\Phi := \varphi(H \cdot)\),
where \(H \in \mathbb{R}^{n,n}\) and \(\varphi: \mathbb R^n \rightarrow \mathbb{R} \cup \{+\infty\} \)
meet certain requirements which are often fulfilled in image processing models.
In this case we prove by incorporating the dual problems
that there exists a bijective function
such that
the solutions of the constrained problem coincide with those of the
penalized problem if and only if \(\tau\) and \(\lambda\) are in the graph
of this function.
We illustrate the relation between \(\tau\) and \(\lambda\) for various problems
arising in image processing.
In particular, we point out the relation to the Pareto frontier for joint sparsity problems.
We demonstrate the performance of the
constrained model in restoration tasks of images corrupted by Poisson noise
with the \(I\)-divergence as data fitting term \(\varphi\)
and in inpainting models with the constrained nuclear norm.
Such models can be useful if we have a priori knowledge on the image rather than on the noise level.

The safety of embedded systems is becoming more and more important nowadays. Fault Tree Analysis (FTA) is a widely used technique for analyzing the safety of embedded systems. A standardized tree-like structure called a Fault Tree (FT) models the failures of the systems. The Component Fault Tree (CFT) provides an advanced modeling concept for adapting the traditional FTs to the hierarchical architecture model in system design. Minimal Cut Set (MCS) analysis is a method that works for qualitative analysis based on the FTs. Each MCS represents a minimal combination of component failures of a system called basic events, which may together cause the top-level system failure. The ordinary representations of MCSs consist of plain text and data tables with little additional supporting visual and interactive information. Importance analysis based on FTs or CFTs estimates the contribution of each potential basic event to a top-level system failure. The resulting importance values of basic events are typically represented in summary views, e.g., data tables and histograms. There is little visual integration between these forms and the FT (or CFT) structure. The safety of a system can be improved using an iterative process, called the safety improvement process, based on FTs taking relevant constraints into account, e.g., cost. Typically, relevant data regarding the safety improvement process are presented across multiple views with few interactive associations. In short, the ordinary representation concepts cannot effectively facilitate these analyses.
We propose a set of visualization approaches for addressing the issues above mentioned in order to facilitate those analyses in terms of the representations.
Contribution:
1. To support the MCS analysis, we propose a matrix-based visualization that allows detailed data of the MCSs of interest to be viewed while maintaining a satisfactory overview of a large number of MCSs for effective navigation and pattern analysis. Engineers can also intuitively analyze the influence of MCSs of a CFT.
2. To facilitate the importance analysis based on the CFT, we propose a hybrid visualization approach that combines the icicle-layout-style architectural views with the CFT structure. This approach facilitates to identify the vulnerable components taking the hierarchies of system architecture into account and investigate the logical failure propagation of the important basic events.
3. We propose a visual safety improvement process that integrates an enhanced decision tree with a scatter plot. This approach allows one to visually investigate the detailed data related to individual steps of the process while maintaining the overview of the process. The approach facilitates to construct and analyze improvement solutions of the safety of a system.
Using our visualization approaches, the MCS analysis, the importance analysis, and the safety improvement process based on the CFT can be facilitated.

The scientific aim of this work was to synthesize and characterize new bidentate and tridentate phosphine ligands , their corresponding palladium complexes and to examine their application as homogenous catalysts. Later on, a part of the obtained palladium catalysts was immobilized and used as heterogonous catalyst.
Pyrimidinyl functionalized diphenyl phosphine ligands were synthesized by ring closure of [2-(3-dimethylamino-1-oxoprop-2-en-yl)phenyl]diphenylphosphine with an excess of substituted guanidinium salts. Furthermore to increase the electron density at phosphorous centre the two aryl substituents on the phosphanyl group were exchanged against two alkyl substituents. Electron rich pyrimidinyl functionalized dialkyl phosphine ligands were synthesized from pyrimidinyl functionalized bromobenzene in a process involving lithiation followed by reaction with a chlorodialkylphosphine.
Starting from the new synthesized diaryl phosphine ligands, their corresponding palladium complexes were synthesized. I was able to show that slight changes at the amino group of [(2-aminopyrimidin-4-yl)aryl]phosphines lead to pronounced differences in the stability and catalytic activity of the corresponding palladium(II) complexes. Having a P,C coordination mode, the palladium complex can catalyze rapidly the Suzuki coupling reaction of phenylbronic acid with arylbromides even at room temperature with a low loading.
Using the NH2 group of the aminopyrimidine as a potential site for the introduction of an other substituent, bidentate and tridentate ligands containing phosphorous atoms connected to the aminopyrimidine group and their corresponding palladium complexes were synthesized and characterized.
Two ligands [2- and 4-(4-(2-amino)pyrimidinyl)phenyl]diphenylphosphine (containing NH2 group) functionalized with a ethoxysilane group were synthesized. The palladium complexes based on these ligands were prepared and immobilized on commercial silica and MCM-41. Using elemental analysis, FT-IR, solid state 31P, 13C and 29Si CP–MAS NMR spectroscopy, XRD and N2 adsorption the success of the immobilization was confirmed and the structure of the heterogenized catalyst was investigated.
The resulting heterogeneous catalysts were applied for the Suzuki reaction and exhibited excellent activity, selectivity and reusability.

Predicting secondary structures of RNA molecules is one of the fundamental problems of and thus a challenging task in computational structural biology. Existing prediction methods basically use the dynamic programming principle and are either based on a general thermodynamic model or on a specific probabilistic model, traditionally realized by a stochastic context-free grammar. To date, the applied grammars were rather simple and small and despite the fact that statistical approaches have become increasingly appreciated over the past years, a corresponding sampling algorithm based on a stochastic RNA structure model has not yet been devised. In addition, basically all popular state-of-the-art tools for computational structure prediction have the same worst-case time and space requirements of O(n^3) and O(n^2) for sequence length n, limiting their applicability for practical purposes due to the often quite large sizes of native RNA molecules. Accordingly, the prime demand imposed by biologists on computational prediction procedures is to reach a reduced waiting time for results that are not significantly less accurate.
We here deal with all of these issues, by describing algorithms and performing comprehensive studies that are based on sophisticated stochastic context-free grammars of similar complexity as those underlying thermodynamic prediction approaches, where all of our methods indeed make use of the concept of sampling. We also employ the approximation technique known from theoretical computer science in order to reach a heuristic worst-case speedup for RNA folding.
Particularly, we start by describing a way for deriving a sequence-independent random sampler for an arbitrary class of RNAs by means of (weighted) unranking. The resulting algorithm may generate any secondary structure of a given fixed size n in only O(n·log(n)) time, where the results are observed to be accurate, validating its practical applicability.
With respect to RNA folding, we present a novel probabilistic sampling algorithm that generates statistically representative and reproducible samples of the entire ensemble of feasible structures for a particular input sequence. This method actually samples the possible foldings from a distribution implied by a suitable (traditional or length-dependent) grammar. Notably, we also propose several (new) ways for obtaining predictions from generated samples. Both variants have the same worst-case time and space complexities of O(n^3) and O(n^2) for sequence length n. Nevertheless, evaluations of our sampling methods show that they are actually capable of producing accurate (prediction) results.
In an attempt to resolve the long-standing problem of reducing the time complexity of RNA folding algorithms without sacrificing much of the accuracy of the results, we invented an innovative heuristic statistical sampling method that can be implemented to require only O(n^2) time for generating a fixed-size sample of candidate structures for a given sequence of length n. Since a reasonable prediction can still efficiently be obtained from the generated sample set, this approach finally reduces the worst-case time complexity by a liner factor compared to all existing precise methods. Notably, we also propose a novel (heuristic) sampling strategy as opposed to the common one typically applied for statistical sampling, which may produce more accurate results for particular settings. A validation of our heuristic sampling approach by comparison to several leading RNA secondary structure prediction tools indicates that it is capable of producing competitive predictions, but may require the consideration of large sample sizes.