The increasing demand for energy and the pressure to reduce reliance on fossil fuels encourages the development of devices to harness clean and renewable energy. Solar energy is a large enough source to fulfill these demands, however, in order to overcome its daily and seasonal variability, it has been proposed that sunlight be harvested and stored in the form of chemical fuels. One potential approach is the photosynthetic splitting of water to store solar energy in the simplest chemical bond, H–H, using a device that includes: semiconducting microwire arrays as light harvesting components, redox catalysts, and a membrane barrier for separating the products of water redox reactions.. However, the harvested solar energy can be lost across the system and it is critical to characterize the electrical properties of each component within the system to quantify how much of this energy will ultimately be coupled to the water splitting reactions. The aim of this research is to develop approaches for characterization of a proposed system of this kind, incorporating individual semiconductor microwires as photoelectrodes (with no redox catalysts) embedded into a candidate conducting polymer membrane to form a single functional unit. Semiconductor microwires were isolated and using a novel contact formation approach with tungsten probes in a standard probe station, and their current versus voltage properties were characterized. This approach is of particular interest when ii considering the limitations of conventional contact formation approaches (e.g. thermal evaporation of contact metals), arising from the small dimensions of the microwires and also the incompatibility of these techniques with many microwire/polymer structures due to the unwanted interactions between polymers, photoresists, etchants and the high temperature lithographic processes. The electrical properties of different microwires and also the junctions between microwires and two candidate polymers were studied. Specifically, the combination of methyl-terminated silicon microwires and PEDOT:PSS:Nafion demonstrated promising behavior, with a total DC resistance of approximately 720 kΩ (i.e. losses < 16 mV at maximum available photocurrent), making it a suitable candidate for the use in the proposed system. The outcome of these research may be applied to many applications including semiconducting microstructures and conducting polymers.

This thesis describes studies of materials which can be exploited for hydrogen production from water and sunlight. The materials investigated are maghemite (γ-Fe2O3), magnetite (Fe3O4) and especially hematite (α-Fe2O3), which is an iron oxide with most promising properties in this field. Hematite has been deposited using Atomic Layer Deposition (ALD) - a thin-film technique facilitating layer-by-layer growth with excellent thickness control and step coverage. The iron oxides were deposited using bis-cyclopentadienyl iron (Fe(Cp)2) or iron pentacarbonyl (Fe(CO)5) in combination with an O2 precursor. Since it is crucial to have good control of the deposition process, the influence of substrate, process temperature, precursor and carrier gas have been investigated systematically. By careful control of these deposition parameters, three polymorphs of iron oxide could be deposited: hematite (α-Fe2O3), maghemite (γ-Fe2O3) and magnetite (Fe3O4). The deposited materials were characterized using X-ray Diffraction, Raman and UV-VIS Spectroscopy, and Scanning Electron Microscopy. Hard X-ray Photoelectron Spectroscopy (HAXPES) was also used, since it is a non-destructive, chemically specific, surface sensitive technique – the surface sensitivity resulting from the short mean escape depth of the photoelectrons. The depth probed can be controlled by varying the excitation energy; higher photoelectron energies increasing the inelastic mean-free-path in the material. HAXPES studies of atomic diffusion from F-doped SnO2 substrates showed increased doping levels of Sn, Si and F in the deposited films. Diffusion from the substrate was detected at annealing temperatures between 550 °C and 800 °C. Films annealed in air exhibited improved photocatalytic behavior; a photocurrent of 0.23 mA/cm2 was observed for those films, while the as-deposited hematite films showed no photo-activity whatsoever. The optical properties of low-dimensional hematite were studied in a series of ultra-thin films (thicknesses in the 2-70 nm range). The absorption maxima were shifted to higher energies for films thinner than 20 nm, revealing a different electronic structure in thin films.

We design, analyze, and optimize distributed detection and estimation algorithms in a large, shared-channel, single-hop wireless sensor network (WSN). The fusion center (FC) is allocated a shared transmission channel to collect local decisions/estimates but cannot collect all of them because of limited energy, bandwidth, or time. We propose a strategy called reliability-based splitting algorithm that enables the FC to collect local decisions/estimates in descending order of their reliabilities through a shared collision channel. The algorithm divides the transmission channel into time frames and the sensor nodes into groups based on their observation reliabilities. Only nodes with a specified range of reliabilities compete for the channel using slotted ALOHA within each frame. Nodes with the most reliable decisions/estimates attempt transmission in the first frame; nodes with the next most reliable set of decisions/estimates attempt in the next frame; etc. The reliability-based splitting algorithm is applied in three scenarios: time-constrained distributed detection; sequential distributed detection; and time-constrained estimation. Performance measures of interest - including detection error probability, efficacy, asymptotic relative efficiency, and estimator variance - are derived. In addition, we propose and analyze algorithms that exploit information from the occurrence of collisions to improve the performance of both time-constrained distributed detection and sequential distributed detection.

The problem of reconstruction of digital images from their degraded measurements has always been a problem of central importance in numerous applications of imaging sciences. In real life, acquired imaging data is typically contaminated by various types of degradation phenomena which are usually related to the imperfections of image acquisition devices and/or environmental effects. Accordingly, given the degraded measurements of an image of interest, the fundamental goal of image reconstruction is to recover its close approximation, thereby "reversing" the effect of image degradation. Moreover, the massive production and proliferation of digital data across different fields of applied sciences creates the need for methods of image restoration which would be both accurate and computationally efficient. Developing such methods, however, has never been a trivial task, as improving the accuracy of image reconstruction is generally achieved at the expense of an elevated computational burden. Accordingly, the main goal of this thesis has been to develop an analytical framework which allows one to tackle a wide scope of image reconstruction problems in a computationally efficient manner. To this end, we generalize the concept of variable splitting, as a tool for simplifying complex reconstruction problems through their replacement by a sequence of simpler and therefore easily solvable ones. Moreover, we consider two different types of variable splitting and demonstrate their connection to a number of existing approaches which are currently used to solve various inverse problems. In particular, we refer to the first type of variable splitting as Bregman Type Splitting (BTS) and demonstrate its applicability to the solution of complex reconstruction problems with composite, cross-domain constraints. As specific applications of practical importance, we consider the problem of reconstruction of diffusion MRI signals from sub-critically sampled, incomplete data as well as the problem of blind deconvolution of medical ultrasound images. Further, we refer to the second type of variable splitting as Fuzzy Clustering Splitting (FCS) and show its application to the problem of image denoising. Specifically, we demonstrate how this splitting technique allows us to generalize the concept of neighbourhood operation as well as to derive a unifying approach to denoising of imaging data under a variety of different noise scenarios.

Bewehrungen mit einer hochmoduligen Polymertränkung erreichen im Betonbauteil Textilspannungen von über 1200 N/mm². Ab diesem Niveau wurden in Dehnkörperversuchen Längsrisse und Betonabplatzungen beobachtet. Für die Eingrenzung und Identifikation der elementaren, verantwortlichen Mechanismen weisen großformatige Dehnkörper störende Einflüsse von Randeffekten und Imperfektionen auf. Daher wurde ein neuer Versuchsaufbau entwickelt, bestehend aus einem in einen Betonquader eingebetteten Einzelroving. Die simple Herstellung und die Verlässlichkeit dieser Kategorie von Experimenten in Bezug auf die Reproduzierbarkeit und der geringen Streuung der Resultate machen sie zu einer robusten Grundlage für experimentelle Untersuchungen des Verhaltens von TRC. Die experimentell ermittelten Bruchlasten werden zunächst bezüglich ihrer Leistung diskutiert und dann die beobachteten Bruchvorgänge kategorisiert hinsichtlich kompatibler mechanischer Hypothesen für die Initiierung von Längsrissen und des Spaltversagen. / Reinforcements with a high-modulus, polymeric impregnation achieve textile tensions of 1200 N/mm² and more in concrete parts. Starting at this level longitudinal cracks and splitting were observed in tests. In order to isolate and identify the fundamental, responsible mechanisms large-scale specimen show an interfering impact of boundary effects and imperfections. Therefore a new test set-up was developed, consisting of a single roving embedded in a single concrete cuboid. The simplicity of production and reliability of this class of experiments in terms of repeatability and low scatter of results makes them a robust basis for experimental investigation of TRC behavior. The experimentally obtained strengths are discussed in terms of the performance, followed by the categorization of observed failure patterns with respect to the available mechanical hypotheses of the longitudinal crack initiation and splitting failure.

京都大学 / 新制・課程博士 / 博士(工学) / 甲第23914号 / 工博第5001号 / 新制||工||1781(附属図書館) / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 阿部 竜, 教授 安部 武志, 教授 作花 哲夫 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

Duisburg, Essen, Univ., Diss., 2005

Την 8η Ιουνίου 2008, στις 15:25 τοπική ώρα (12:25 GMT) ένας σεισμός μεγέθους Mw 6.4 εκδηλώθηκε στη ΒΔ Πελοπόννησο, στη Δυτική Ελλάδα. Το επίκεντρο προσδιορίστηκε κοντά στο χωριό Μιχόι, στη Δημοτική Ενότητα Μόβρης, περίπου 35 km ΝΔ της Πάτρας. Στην παρούσα εργασία, έγινε μία μελέτη ανισοτροπίας στην επικεντρική περιοχή του σεισμού της 8ης Ιουνίου. Συγκεκριμένα, έγινε μία μελέτη για την ανίχνευση του φαινομένου διαχωρισμού των εγκαρσίων κυμάτων και της εξέλιξής του σε σχέση με την εκδήλωση του σεισμού της 8ης Ιουνίου. Χρησιμοποιήθηκαν οι καταγραφές από τον σεισμολογικό σταθμό του Ριόλου (RLS), καθώς είναι ο μόνος κοντινός σταθμός στο επίκεντρο του σεισμού της 8ης Ιουνίου που βρισκόταν σε συνεχή λειτουργία κατά τα χρονικά διαστήματα πριν και μετά την εκδήλωση του σεισμού. Για τη μελέτη του φαινομένου του διαχωρισμού των εγκαρσίων κυμάτων χρησιμοποιήθηκε η μέθοδος cross-correlation (Ando et al., 1983; Fukao, 1984). Μετά την επεξεργασία των δεδομένων, προσδιορίστηκαν οι παράμετροι του φαινομένου, φ (διεύθυνση ταλάντωσης της ταχύτερης συνιστώσας των εγκαρσίων κυμάτων) και dt (χρόνος καθυστέρησης μεταξύ των δύο συνιστωσών) για κάθε ένα σεισμικό γεγονός. Ο διαχωρισμός των εγκαρσίων κυμάτων (shear-wave splitting) είναι ένα φαινόμενο κατά το οποίο, τα εγκάρσια κύματα διαχωρίζονται σε δύο συνιστώσες, με διαφορετικές διευθύνσεις πόλωσης και διαφορετικές ταχύτητες διάδοσης. Ο διαχωρισμός αυτός πραγματοποιείται κατά την διάδοση των εγκαρσίων κυμάτων μέσα από ένα ανισοτροπικό μέσο (Crampin and Chastin, 2003; Crampin and Peacock, 2005). Σύμφωνα με τη θεωρία, ο διαχωρισμός των εγκαρσίων κυμάτων στον φλοιό, προκαλείται εξαιτίας της ύπαρξης μικρο-ρωγμών, μικρο-διαρρήξεων κορεσμένων με ρευστά. Οι μικρο-διαρήξεις αυτές έχουν συνήθως διευθύνσεις παράλληλες ή υπό-παράλληλες με αυτή της μέγιστης οριζόντιας συμπιεστικής τάσης σε μία περιοχή (Crampin, 1993). Η ανάλυση των δεδομένων κατέδειξε την ύπαρξη του φαινομένου διαχωρισμού των εγκαρσίων κυμάτων στην υπό μελέτη περιοχή. Τόσο πριν, όσο και μετά την εκδήλωση του σεισμού της 8ης Ιουνίου, οι διευθύνσεις πόλωσης της ταχύτερης συνιστώσας των εγκαρσίων κυμάτων ακολουθούν μία μέση διεύθυνση ΒΒΔ-ΝΝΑ. Η μέση διεύθυνση της ταχύτερης συνιστώσας δεν είναι σύμφωνη με τα χαρακτηριστικά του πεδίου των τάσεων στην περιοχή, όπως προσδιορίστηκαν από τους Konstantinou et al. (2011) και Hollenstein et al. (2008), με μία μέση διεύθυνση οριζόντιας συμπιεστικής τάσης Α-Δ. Η ΒΒΔ-ΝΝΑ διεύθυνση πόλωσης της ταχύτερης συνιστώσας οφείλεται πιθανόν στη δράση ενός πεδίου τάσεων γύρω και κάτω από τη θέση καταγραφής με τοπικά χαρακτηριστικά. Τέλος, παρατηρήθηκε μία αύξηση στις τιμές των χρόνων καθυστέρησης μετά την εκδήλωση του σεισμού της 8ης Ιουνίου. Η μέση τιμή των χρόνων καθυστέρησης πριν την εκδήλωση του σεισμού ήταν περίπου 27.3 ms, ενώ μετά την εκδήλωσή του 41.7 ms. H αύξηση των χρόνων καθυστέρησης, υποδηλώνει μία μεταβολή των ιδιοτήτων του μέσου στον ανώτερο φλοιό εξαιτίας της εκδήλωσης του σεισμού. Η εκδήλωση του σεισμού της 8ης Ιουνίου προκάλεσε πιθανόν την διεύρυνση και την επιμήκυνση των προϋπαρχόντων μικρο-διαρρήξεων του φλοιού, τη δημιουργία νέων και την επιπλέον πλήρωσή τους με ρευστά. / On June 8, 2008, at 15:25 local time (12:25 GMT) an Mw 6.4 earthquake occurred in the area of northwest Peloponnesus, Western Greece. The epicenter was located near Mihoi village, in the municipality of Movri, about 35 km southwest of Patras. In this paper, a crustal anisotropy analysis was performed in the epicentral area of Movri Mountain earthquake. Specifically, there was a study to detect shear-wave splitting phenomenon and its temporal evolution in relation to the occurrence of Movri Mountain earthquake. For the needs of the study, we used seismic records from the seismological station of Riolos (RLS). Riolos station is the nearest station from the epicenter of Movri Mountain earthquake which was in continuous operation during the periods before and after the occurrence of the earthquake. The method that was used to study shear-wave splitting phenomenon was the cross-correlation method (Ando et al., 1983; Fukao, 1984; Kuo et al., 1994). Through the data processing, splitting parameters φ (polarization direction of the fastest component of shear waves) and dt (time delay between the two components) were measured for each seismic event. Shear-wave splitting is a phenomenon in which shear-waves are separated into two components with different polarization directions and velocities. The phenomenon in the upper crust is caused by the existence of stress-aligned, fluid-filled micro-cracks/micro-fractures. The polarization directions of the fast components are usually parallel or sub-parallel to the direction of the maximum horizontal compressive stress (Crampin, 1993). Data analysis revealed the existence of shear-wave splitting phenomenon in the study area. Both before and after the occurrence of Movri Mountain earthquake, the polarization directions of the fast component of shear waves follow a general NNW-SSE direction. The observed mean fast polarization direction is not consistent with the estimated characteristics of the regional stress field of the broader area, as identified by Kontsantinou et al. (2011) and Hollenstein et al. (2008), who report a general E-W direction of the maximum horizontal compressive stress. The difference between the estimated fast polarization directions and the properties of the regional stress field shows the presence of a local stress field in the study area. Finally, an increase in time delays was observed after the occurrence of Movri Mountain earthquake. The average value of delay times before the occurrence of the earthquake was about 27.3ms, while after the occurrence was about 41.7ms. The increase in delay times which was observed after the occurrence of Movri Mountain earthquake possibly indicates changes in the properties of the medium in the upper crust. The occurrence of Movri Mountain earthquake caused the expansion/ lengthening of micro-cracks and its further filling with fluids.

Convex optimization problems are a class of mathematical problems which arise in numerous applications. Although interior-point methods can in principle solve these problems efficiently, they may become intractable for solving large-scale problems or be unsuitable for real-time embedded applications. Iterations of operator splitting methods are relatively simple and computationally inexpensive, which makes them suitable for these applications. However, some of their known limitations are slow asymptotic convergence, sensitivity to ill-conditioning, and inability to detect infeasible problems. The aim of this thesis is to better understand operator splitting methods and to develop reliable software tools for convex optimization. The main analytical tool in our investigation of these methods is their characterization as the fixed-point iteration of a nonexpansive operator. The fixed-point theory of nonexpansive operators has been studied for several decades. By exploiting the properties of such an operator, it is possible to show that the alternating direction method of multipliers (ADMM) can detect infeasible problems. Although ADMM iterates diverge when the problem at hand is unsolvable, the differences between subsequent iterates converge to a constant vector which is also a certificate of primal and/or dual infeasibility. Reliable termination criteria for detecting infeasibility are proposed based on this result. Similar ideas are used to derive necessary and sufficient conditions for linear (geometric) convergence of an operator splitting method and a bound on the achievable convergence rate. The new bound turns out to be tight for the class of averaged operators. Next, the OSQP solver is presented. OSQP is a novel general-purpose solver for quadratic programs (QPs) based on ADMM. The solver is very robust, is able to detect infeasible problems, and has been extensively tested on many problem instances from a wide variety of application areas. Finally, operator splitting methods can also be effective in nonconvex optimization. The developed algorithm significantly outperforms a common approach based on convex relaxation of the original nonconvex problem.

O processo de especiação é lento e gradual e a não completa compreensão deste processo ao longo da história do conhecimento nos remete a problemas clássicos sobre a classificação dos organismos. Neste trabalho, conduzimos um estudo sobre os padrões filogeográficos e evolutivos de duas espécies irmãs parapátricas de sapinhos de barriga-vermelha Melanophryniscus dorsalis e M. montevidensis, listadas como mundialmente ameaçadas segundo a IUCN , além de um estudo aplicado com o uso de modelos de nicho ecológico identificando áreas de interesse a conservação para ambas as espécies. Através dos modelos consensos baseados nos algoritmos BIOCLIM, GARP e Máxima entropia e da análise de “Hotspot” áreas de alta adequabilidade ambiental foram identificadas para ambas as espécies. A validação em campo de modelos preliminares indicou a ausência de indivíduos em locais de alta adequabilidade. Expedições a campo também revelaram uma série de novos pontos de ocorrência, entre os limites da distribuição, e a confirmação de registros historicamente omitidos por listas regionais, nacional e mundial de espécies ameaçadas. Para este estudo propomos cinco “hotspots” de grande interesse na conservação e preservação de ambas as espécies. Os dados moleculares, obtidos através do Cytb e COI, indicam claramente um processo de especiação ocorrendo com M. dorsalis e M. montevidensis com um ancestral comum para ambas as espécies datando entre 3 e 3,5 milhões de anos. A rede da haplótipos, para ambas as espécies nos dois marcadores, é do tipo estrela com um haplótipo central e uma série de outros com uma ou poucas mutações partindo do haplótipo central, indicando expansão demográfica e também demonstrando alta variabilidade. A população mais ao norte de M. dorsalis, na localidade de Mar Grosso no município de Laguna (SC), merece uma atenção especial por se tratar de uma Unidade de Manejo (UM) por seus indivíduos apresentarem uma viii frequência única de alelos. Segundo a definição de UM, a estratégia indicada para esta população é a delimitação de uma área específica e monitoramento da população. Os resultados obtidos neste trabalho provêm um conjunto de informações importantes em nível específico para a implementação de um banco de dados nacional sobre espécies ameaçadas. Os dados gerados neste estudo também serão integrados ao Plano Nacional de Ação para a conservação e preservação dos anfíbios e répteis ameaçados de extinção da região sul do Brasil (PAN SUL) gerido pelo Instituto Chico Mendes de conservação da Biodiversidade. / The speciation process is commonly slow and gradual and the incompletely understand of this process throughout the history of knowledge leads us to the classic problems of the organism classification. In this work, we conducted a study on the phylogeographic and evolutionary patterns of two parapatric sister species of red-bellied-toads Melanophryniscus dorsalis and M. montevidensis, listed as globally threatened according to the IUCN, as well as an applied study using ecological niche models to identify areas for conservation interest for both species. Through consensus models based on algorithms BIOCLIM, GARP and Maximum Entropy and the hotspot analysis, areas of high environmental suitability were identified for both species. Field validation of preliminary models also indicated the absence of individuals in areas of high suitability. Field expeditions also revealed new occurrence points within the boundaries of the distribution, and confirmation records historically omitted by regional, national and global lists of threatened species. For this study we propose five hotspots of great interest in the conservation and preservation of both species. Molecular data obtained through Cytb and COI, clearly indicate the speciation process occurring with M. dorsalis and M. montevidensis with a common ancestor to both species dated between 3 and 3.5 million years. The haplotype network for both markers in both species are star-like which consist of a center haplotype with a series of haplotyps with one or few mutations starting from the central haplotype indicates demographic expansion and also shows high variability. The north population found in M. dorsalis, at the locality of Mar Grosso in the city of Laguna, needs special attention because it is a Management Unit (MU) by his individuals present a single frequency alleles. According to the definition of MU, the strategy indicated for this population is the delimitation of a specific area and population monitoring. x The results obtained in this study provide important information set on specific level for the implementation of a national database on endangered species. The generated data in this study will also be integrated into the National Plan of Action for the conservation and preservation of reptiles and amphibians threatened by extinction in southern Brazil (PAN SUL) managed by the Chico Mendes Institute for Biodiversity Conservation.