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This thesis addresses real-time rendering techniques for 3D information lenses based on the focus & context metaphor. It analyzes, conceives, implements, and reviews its applicability to objects and structures of virtual 3D city models. In contrast to digital terrain models, the application of focus & context visualization to virtual 3D city models is barely researched. However, the purposeful visualization of contextual data of is extreme importance for the interactive exploration and analysis of this field. Programmable hardware enables the implementation of new lens techniques, that allow the augmentation of the perceptive and cognitive quality of the visualization compared to classical perspective projections. A set of 3D information lenses is integrated into a 3D scene-graph system: • Occlusion lenses modify the appearance of virtual 3D city model objects to resolve their occlusion and consequently facilitate the navigation. • Best-view lenses display city model objects in a priority-based manner and mediate their meta information. Thus, they support exploration and navigation of virtual 3D city models. • Color and deformation lenses modify the appearance and geometry of 3D city models to facilitate their perception. The presented techniques for 3D information lenses and their application to virtual 3D city models clarify their potential for interactive visualization and form a base for further development.
This thesis provides a novel view on the early stage of crystallization utilizing calcium carbonate as a model system. Calcium carbonate is of great economical, scientific and ecological importance, because it is a major part of water hardness, the most abundant Biomineral and forms huge amounts of geological sediments thus binding large amounts of carbon dioxide. The primary experiments base on the evolution of supersaturation via slow addition of dilute calcium chloride solution into dilute carbonate buffer. The time-dependent measurement of the Ca2+ potential and concurrent pH = constant titration facilitate the calculation of the amount of calcium and carbonate ions bound in pre-nucleation stage clusters, which have never been detected experimentally so far, and in the new phase after nucleation, respectively. Analytical Ultracentrifugation independently proves the existence of pre-nucleation stage clusters, and shows that the clusters forming at pH = 9.00 have a proximately time-averaged size of altogether 70 calcium and carbonate ions. Both experiments show that pre-nucleation stage cluster formation can be described by means of equilibrium thermodynamics. Effectively, the cluster formation equilibrium is physico-chemically characterized by means of a multiple-binding equilibrium of calcium ions to a ‘lattice’ of carbonate ions. The evaluation gives GIBBS standard energy for the formation of calcium/carbonate ion pairs in clusters, which exhibits a maximal value of approximately 17.2 kJ mol^-1 at pH = 9.75 and relates to a minimal binding strength in clusters at this pH-value. Nucleated calcium carbonate particles are amorphous at first and subsequently become crystalline. At high binding strength in clusters, only calcite (the thermodynamically stable polymorph) is finally obtained, while with decreasing binding strength in clusters, vaterite (the thermodynamically least stable polymorph) and presumably aragonite (the thermodynamically intermediate stable polymorph) are obtained additionally. Concurrently, two different solubility products of nucleated amorphous calcium carbonate (ACC) are detected at low binding strength and high binding strength in clusters (ACC I 3.1EE-8 M^2, ACC II 3.8EE-8 M^2), respectively, indicating the precipitation of at least two different ACC species, while the clusters provide the precursor species of ACC. It is proximate that ACC I may relate to calcitic ACC –i.e. ACC exhibiting short range order similar to the long range order of calcite and that ACC II may relate to vateritic ACC, which will subsequently transform into the particular crystalline polymorph as discussed in the literature, respectively. Detailed analysis of nucleated particles forming at minimal binding strength in clusters (pH = 9.75) by means of SEM, TEM, WAXS and light microscopy shows that predominantly vaterite with traces of calcite forms. The crystalline particles of early stages are composed of nano-crystallites of approximately 5 to 10 nm size, respectively, which are aligned in high mutual order as in mesocrystals. The analyses of precipitation at pH = 9.75 in presence of additives –polyacrylic acid (pAA) as a model compound for scale inhibitors and peptides exhibiting calcium carbonate binding affinity as model compounds for crystal modifiers- shows that ACC I and ACC II are precipitated in parallel: pAA stabilizes ACC II particles against crystallization leading to their dissolution for the benefit of crystals that form from ACC I and exclusively calcite is finally obtained. Concurrently, the peptide additives analogously inhibit the formation of calcite and exclusively vaterite is finally obtained in case of one of the peptide additives. These findings show that classical nucleation theory is hardly applicable for the nucleation of calcium carbonate. The metastable system is stabilized remarkably due to cluster formation, while clusters forming by means of equilibrium thermodynamics are the nucleation relevant species and not ions. Most likely, the concept of cluster formation is a common phenomenon occurring during the precipitation of hardly soluble compounds as qualitatively shown for calcium oxalate and calcium phosphate. This finding is important for the fundamental understanding of crystallization and nucleation-inhibition and modification by additives with impact on materials of huge scientific and industrial importance as well as for better understanding of the mass transport in crystallization. It can provide a novel basis for simulation and modelling approaches. New mechanisms of scale formation in Bio- and Geomineralization and also in scale inhibition on the basis of the newly reported reaction channel need to be considered.
Nanostructured inorganic materials are routinely synthesized by the use of templates. Depending on the synthesis conditions of the product material, either “soft” or “hard” templates can be applied. For sol-gel processes, usually “soft” templating techniques are employed, while “hard” templates are used for high temperature synthesis pathways. In classical templating approaches, the template has the unique role of structure directing agent, in the sense that it is not participating to the chemical formation of the resulting material. This work investigates a new templating pathway to nanostructured materials, where the template is also a reagent in the formation of the final material. This concept is described as “reactive templating” and opens a synthetic path toward materials which cannot be synthesised on a nanometre scale by classical templating approaches. Metal nitrides are such kind of materials. They are usually produced by the conversion of metals or metal oxides in ammonia flow at high temperature (T > 1000°C), which make the application of classical templating techniques difficult. Graphitic carbon nitride, g-C3N4, despite its fundamental and theoretical importance, is probably one of the most promising materials to complement carbon in material science and many efforts are put in the synthesis of this material. A simple polyaddition/elimination reaction path at high temperature (T = 550°C) allows the polymerisation of cyanamide toward graphitic carbon nitride solids. By hard templating, using nanostructured silica or aluminium oxide as nanotemplates, a variety of nanostructured graphitic carbon nitrides such as nanorods, nanotubes, meso- and macroporous powders could be obtained by nanocasting or nanocoating. Due to the special semi-conducting properties of the graphitic carbon nitride matrix, the nanostructured graphitic carbon nitrides show unexpected catalytic activity for the activation of benzene in Friedel-Crafts type reactions, making this material an interesting metal free catalyst. Furthermore, due to the chemical composition of g-C3N4 and the fact that it is totally decomposed at temperatures between 600°C and 800°C even under inert atmosphere, g-C3N4 was shown to be a good nitrogen donor for the synthesis of early transition metal nitrides at high temperatures. Thus using the nanostructured carbon nitrides as “reactive templates” or “nanoreactors”, various metal nitride nanostructures, such as nanoparticles and porous frameworks could be obtained at high temperature. In this approach the carbon nitride nanostructure played both the role of the nitrogen source and of the exotemplate, imprinting its size and shape to the resulting metal nitride nanostructure.
For the first time stabilizer-free vinylidene fluoride (VDF) polymerizations were carried out in homogeneous phase with supercritical CO₂. Polymerizations were carried out at 140°C, 1500 bar and were initiated with di-tert-butyl peroxide (DTBP). In-line FT-NIR (Fourier Transform- Near Infrared) spectroscopy showed that complete monomer conversion may be obtained. Molecular weights were determined via size-exclusion chromatography (SEC) and polymer end group analysis by 1H-NMR spectroscopy. The number average molecular weights were below 104 g∙mol−1 and polydispersities ranged from 3.1 to 5.7 depending on DTBP and VDF concentration. To allow for isothermal reactions high CO₂ contents ranging from 61 to 83 wt.% were used. The high-temperature, high-pressure conditions were required for homogeneous phase polymerization. These conditions did not alter the amount of defects in VDF chaining. Scanning electron microscopy (SEM) indicated that regular stack-type particles were obtained upon expansion of the homogeneous polymerization mixture. To reduce the required amount of initiator, further VDF polymerizations using chain transfer agents (CTAs) to control molecular weights were carried out in homogeneous phase with supercritical carbon dioxide (scCO₂) at 120 °C and 1500 bar. Using perfluorinated hexyl iodide as CTA, polymers of low polydispersity ranging from 1.5 to 1.2 at the highest iodide concentration of 0.25 mol·L-1 were obtained. Electrospray ionization- mass spectroscopy (ESI-MS) indicates the absence of initiator derived end groups, supporting livingness of the system. The “livingness” is based on the labile C-I bond. However, due to the weakness of the C-I bond perfluorinated hexyl iodide also contributes to initiation. To allow for kinetic analyses of VDF polymerizations the CTA should not contribute to initiation. Therefore, additional CTAs were applied: BrCCl3, C6F13Br and C6F13H. It was found that C6F13H does not contribute to initiation. At 120°C and 1500 bar kp/kt0.5~ 0.64 (L·mol−1·s−1)0.5 was derived. The chain transfer constant (CT) at 120°C has been determined to be 8·10−1, 9·10−2 and 2·10−4 for C6F13I, C6F13Br and C6F13H, respectively. These CT values are associated with the bond energy of the C-X bond. Moreover, the labile C-I bond allows for functionalization of the polymer to triazole end groups applying click reactions. After substitution of the iodide end group by an azide group 1,3 dipolar cycloadditions with alkynes yield polymers with 1,2,3 triazole end groups. Using symmetrical alkynes the reactions may be carried out in the absence of any catalyst. This end-functionalized poly (vinylidene fluoride) (PVDF) has higher thermal stability as compared to the normal PVDF. PVDF samples from homogeneous phase polymerizations in supercritical CO₂ and subsequent expansion to ambient conditions were analyzed with respect to polymer end groups, crystallinity, type of polymorphs and morphology. Upon expansion the polymer was obtained as white powder. Scanning electron microscopy (SEM) showed that DTBP derived polymer end groups led to stack-type particles whereas sponge- or rose-type particles were obtained in case of CTA fragments as end groups. Fourier-Transform Infrared spectroscopy and wide angle X-ray diffraction indicated that the type of polymorph, α or β crystal phase was significantly affected by the type of end group. The content of β-phase material, which is responsible for piezoelectricity of PVDF, is the highest for polymer with DTBP-derived end groups. In addition, the crystallinity of the material, as determined via differential scanning calorimetry is affected by the end groups and polymer molecular weights. For example, crystallinity ranges from around 26 % for DTBP-derived end groups to a maximum of 62 % for end groups originating from perfluorinated hexyl iodide for polymers with Mn ~2200 g·mol–1. Expansion of the homogeneous polymerization mixture results in particle formation by a non-optimized RESS (Rapid Expansion from Supercritical Solution) process. Thus, it was tested how polymer end groups affect the particles size distribution obtained from RESS process under controlled conditions (T = 50°C and P = 200 bar). In all RESS experiments, small primary PVDF with diameters less than 100 nm without the use of liquid solvents, surfactants, or other additives were produced. A strong correlation between particle size and particle size distribution with polymer end groups and molecular weight of the original material was observed. The smallest particles were found for RESS of PVDF with Mn~ 4000 g·mol–1 and PFHI (C6F13I) - derived end groups.
Landscapes evolve in a complex interplay between climate and tectonics. Thus, the geomorphic characteristics of a landscape can only be understood if both, climatic and tectonic signals of past and ongoing processes can be identified. In order to evaluate the impact of both forcing factors it is crucial to quantify the evolution of geomorphic markers in natural environments. The Cenozoic Andes are an ideal setting to evaluate tectonic and climatic aspects of landscape evolution at different time and length scales in different natural compartments. The Andean Cordillera constitutes the type subduction orogen and is associated with the subduction of the oceanic Nazca Plate beneath the South American continent since at least 200 million years. In Chile and the adjacent regions this convergent margin is characterized by active tectonics, volcanism, and mountain building. Importantly, along the coast of Chile megathrust earthquakes occur frequently and influence landscape evolution. In fact, the largest earthquake ever recorded occurred in south-central Chile in 1960 and comprised a rupture zone of ~ 1000 km length. However, on longer time scales beyond historic documentation of seismicity it is not well known, how such seismotectonic segments have behaved and how they influence the geomorphic evolution of the coastal realms. With several semi-independent morphotectonic segments, recurrent megathrust earthquakes, and a plethora of geomorphic features indicating sustained tectonism, the margin of Chile is thus a key area to study relationships between surface processes and tectonics. In this study, I combined geomorphology, geochronology, sedimentology, and morphometry to quantify the Pliocene-Pleistocene landscape evolution of the tectonically active south-central Chile forearc. Thereby, I provide (1) new results about the influence of seismotectonic forearc segmentation on the geomorphic evolution and (2) new insights in the interaction between climate and tectonics with respect to the morphology of the Chilean forearc region. In particular, I show that the forearc is characterized by three long-term segments that are not correlated with short-lived earthquake-rupture zones that may. These segments are the Nahuelbuta, Toltén, and Bueno segments, each recording a distinct geomorphic and tectonic evolution. The Nahuelbuta and Bueno segments are undergoing active tectonic uplift. The long-term behavior of these two segments is manifested in form of two doubly plunging, growing antiforms that constitute an integral part of the Coastal Cordillera and record the uplift of marine and river terraces. In addition, these uplifting areas have caused major changes in flow directions or rivers. In contrast, the Toltén segment, situated between the two other segments, appears to be quasi-stable. In order to further quantify uplift and incision in the actively deforming Nahuelbuta segment, I dated an erosion surface and fluvial terraces in the Coastal Cordillera with cosmogenic 10Be and 26Al and optically stimulated luminescence, respectively. According to my results, late Pleistocene uplift rates corresponding to 0.88 mm a-1 are faster than surface-uplift rates averaging over the last 5 Ma, which are in the range of 0.21 mm a-1. This discrepancy suggests that surface uplift is highly variable in time and space and might preferably concentrate along reverse faults as indicated by a late Pleistocene flow reversal. In addition, the results of exposure dating with cosmogenic 10Be and 26Al indicate that the morphotectonic segmentation of this region of the forearc has been established in Pliocene time, coeval with the initiation of uplift of the Coastal Cordillera about 5 Ma ago, inferred to be related to a shift in subduction mode from erosion to accretion. Finally, I dated volcanic clasts obtained from alluvial surfaces in the Central Depression, a low-relief sector separating the Coastal from the Main Cordillera, with stable cosmogenic 3He and 21Ne, in order to reveal the controls of sediment accumulation in the forearc. My results document that these gently sloping surfaces have been deposited 150 to 300 ka ago. This deposition may be related to changes in the erosional regime during glacial episodes. Taken together, the data indicates that the overall geomorphic expression of the forearc is of post-Miocene age and may be intimately related to a climatic overprint of the tectonic system. This climatic forcing is also reflected in the topography and local relief of the Central and Southern Andes that vary considerably along the margin, determined by the dominant surface process that in turn is eventually controlled by climate. However, relief also partly reflects surface processes that have taken place under past climatic conditions. This emphasizes that due care has to be exercised when interpreting landscapes as mirrors of modern climates.
This paper compares police reforms during democratization in Poland, Hungary, and Bosnia-Herzegovina. It analyses the changes to the structure of the democratic control of the police in each reform, paying special attention to the decentralization versus centralization aspect of it. The research question of this paper is: Why are some states decentralizing the democratic control of the police, while others are centralizing it, both with the aim of democratization? The theoretical background of this study are theories about policy diffusion and policy transfer. Therefore this study can be categorized as part of two different research areas. On the one hand, it is a paper from the discipline of International Relations. On the other hand, it is a paper from the discipline of Comparative Politics. The combined attention to international and national factors influencing police reform is reflected by the structure of this paper. Chapter 3 examines police structures and police reforms in established democracies as possible role models for new democracies. Chapter 4 looks at international and transnational actors that actively try to influence police reform. After having examined these external factors, three cases of police reform in new democracies are examined in chapter 5.
The arctic region is undergoing the most rapid environmental change experienced on Earth, and the rate of change is expected to increase over the coming decades. Arctic coasts are particularly vulnerable because they lie at the interface between terrestrial systems dominated by permafrost and marine systems dominated by sea ice. An increased rise in sea level and degradation of sea-ice as predicted by the Intergovernmental Panel on Climate Change in its most recent report and as observed recently in the Arctic will likely result in greater rates of coastal retreat. An increase in coastal erosion would result in dramatic increases in the volume of sediment, organic carbon and contaminants to the Arctic Ocean. These in turn have the potential to create dramatic changes in the geochemistry and biodiversity of the nearshore zone and affect the Arctic Ocean carbon cycle. To calculate estimates of organic carbon input from coastal erosion to the Arctic Ocean, current methods rely on the length of the coastline in the form of non self-similar line datasets. This thesis however emphasizes that using shorelines drawn at different scales can induce changes in the amount of sediment released by 30% in some cases. It proposes a substitute method of computations of erosion based on areas instead of lengths (i.e. buffers instead of shoreline lengths) which can be easily implemented at the circum-Arctic scale. Using this method, variations in quantities of eroded sediment are, on average, 70% less affected by scale changes and are therefore a more reliable method of calculation. Current estimates of coastal erosion rates in the Arctic are scarce and long-term datasets are a handful, which complicates assessment and prognosis of coastal processes, in particular the occurrence of coastal hazards. This thesis aims at filling the gap by providing the first long-term dataset (1951-2006) of coastal erosion on the Bykovsky Peninsula, North-East Siberia. This study shows that the coastline, which is made of ice-rich permafrost, retreated at a mean annual rate of 0.59 m/yr between 1951and 2006. Rates were highly variable: 97.0 % of the rates observed were less than 2 m/yr and 81.6% were less than 1m/yr. However, no significant trend in erosion could be recorded despite the study of five temporal subperiods within 1951-2006. The juxtaposition of wind records could not help to explain erosion records either and this thesis emphasizes the local controls on erosion, in particular the cryostratigraphy, the proximity of the Peninsula to the Lena River Delta freshwater plume and the local topographical constraints on swell development. On ice-rich coastal stretches of the Artic, the interaction of coastal dynamics and permafrost leads to the occurrence of spectacular “C-shaped” depressions termed retrogressive thaw slumps which can reach lengths of up to 650 m. On Herschel Island and at King Point (Yukon Coastal Plain, northern Canada), topographical, sedimentological and biogeochemical surveys were conducted to investigate the present and past activity of these landforms. In particular, undisturbed tundra areas were compared with zones of former slump activity, now stabilized and re-vegetated. This thesis shows that stabilized areas are drier and less prone to plant growth than undisturbed areas and feature fundamentally different geotechnical properties. Radiocarbon dating and topographical surveys indicated until up to 300 BP a likely period of dramatic slump activity on Herschel Island, similar to the one currently observed, which led to the creation of these surfaces. This thesis hypothesizes the occurrence of a ~250 years cycle of slump activity on the Herschel Island shoreline based on the surveyed topography and cryostratigraphy and anticipates higher frequency of slump activity in the future. The variety of processes described in this thesis highlights the changing nature of the intensity and frequency of physical processes acting upon the arctic coast. It also challenges current perceptions of the threats to existing industry and community infrastructure in the Arctic. The increasing presence of humans on Artic coasts coupled with the expected development of shipping will drive an increase in economical and industrial activity on these coasts which remains to be addressed scientifically.
In a first step, definitions of the irreducible information structural categories are given, and in a second step, it is shown that there are no invariant phonological or otherwise grammatical correlates of these categories. In other words, the phonology, syntax or morphology are unable to define information structure. It is a common mistake that information structural categories are expressed by invariant grammatical correlates, be they syntactic, morphological or phonological. It is rather the case that grammatical cues help speaker and hearer to sort out which element carries which information structural role, and only in this sense are the grammatical correlates of information structure important. Languages display variation as to the role of grammar in enhancing categories of information structure, and this variation reflects the variation found in the ‘normal’ syntax and phonology of languages.
We propose a definition of aboutness topicality that not only encompasses individual denoting DPs, but also indefinites. We concentrate on the interpretative effects of marking indefinites as topics: they either receive widest scope in their clause, or they are interpreted in the restrictor of an overt or covert Q-adverb. We show that in the first case they are direct aboutness topics insofar as they are the subject of a predication expressed by the comment, while in the second case they are indirect aboutness topics: they define the subject of a higher-order predication – namely the set of situations that the respective Q-adverb quantifies over.