<p>To improve the adsorption capacity of polyacrylonitrile (PAN) fibres, hydrophilic amidoxime fibres were prepared by subsequent conversion of the cyano groups to an amidoxime group by reacting with hydroxylamine at 80&deg / C at an optimum amidoximation time of 2 hrs. The amidoxime fibre was hydrolyzed/alkali treated in a solution of sodium hydroxide to enhance or improve the adsorption properties. This was followed by characterization of the amidoxime and hydrolyzed fibres using Scanning electron microscopy (SEM) / Fourier transform Infrared Spectroscopy (FTIR) and exchange capacity (cationic and anionic). SEM showed that the hydrolysis process made the surface of Amidoxime fibre rougher than that of Polyacrylonitrile fibre. FTIR revealed that the hydrolyzed Amidoxime fibres contained conjugated imine (-C=N-) sequences. Functionalization enhanced the sorption of amidoxime fibres by an increase of 20 % in the cationic exchange capacity. This was achieved by the part conversion of the cyano groups into the carboxylic acid groups. The fibres showed faster kinetics largely due the available exchange sites on the surface of the fibres hence the equilibration was achieved much quicker.</p>

Mindreading is the capacity to attribute psychological states to others and to use those attributions to explain, predict, and understand others’ behaviors. In the past thirty years, mindreading has become the topic of substantial interdisciplinary research and theorizing, with philosophers, psychologists and, more recently, neuroscientists, all contributing to the debate about the nature of the neuropsychological mechanisms that constitute the capacity for mindreading. In this thesis I push this debate forward by using recent results from developmental psychology as the basis for critiques of two prominent views of mindreading. First, I argue that the developmental studies provide evidence of infant mindreading and therefore expose a flaw in José Bermúdez’s view that certain forms of mindreading require language possession. Second, I argue that the evidence of infant mindreading can also be used to undermine Alvin Goldman’s version of Simulation Theory.

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This thesis investigates the strength behavior of a representative highly skewed and horizontally curved bridge as well as analysis and design procedures for these types of structures. The bridge responses at and above a number of limits in the AASHTO (2007) Specifications are considered. The study includes the evaluation of various attributes of the elastic analysis of the subject bridge. These attributes include: (1) the accuracy of 3-D grid versus 3-D FEA models, (2) first-order versus second-order effects during the construction, (3) the ability to predict layover at bearing lines using simplified equations and (4) the benefit of combining the maximum and concurrent major-axis and flange lateral bending values due to live load compared to combining the maximums due to different live loads when checking the section resistances. The study also addresses the ability of different AASHTO 2007 resistance equations to capture the ultimate strength behavior. This is accomplished by comparing the results from full nonlinear 3-D FEA studies to the elastic design and analysis results. Specifically the use of the 2007 AASHTO moment based one-third rule equations is evaluated for composite sections in positive bending.

A three dimensional, Navier-Stokes finite volume flow solver which uses Roe&rsquo / s upwind flux differencing scheme for spatial and Runge-Kutta explicit multi-stage time stepping scheme and implicit Lower-Upper Symmetric Gauss Seidel (LU-SGS) iteration scheme for temporal discretization on unstructured and hybrid meshes is developed for steady rocket internal viscous flow applications. The spatial accuracy of the solver can be selected as first or second order. Second order accuracy is achieved by piecewise linear reconstruction. Gradients of flow variables required for piecewise linear reconstruction are calculated with both Green-Gauss and Least-Squares approaches. The solver developed is first verified against the three-dimensional viscous laminar flow over flat plate. Then the implicit time stepping algorithms are compared against two rocket motor internal flow problems. Although the solver is intended for internal flows, a test case involving flow over an airfoil is also given. As the last test case, supersonic vortex flow between concentric circular arcs is selected.

This thesis explores Chance-Constrained Programming (CCP) in the context of learning. It is shown that chance-constraint approaches lead to improved algorithms for three important learning problems — classification with specified error rates, large dataset classification and Ordinal Regression (OR). Using moments of training data, the CCPs are posed as Second Order Cone Programs (SOCPs). Novel iterative algorithms for solving the resulting SOCPs are also derived. Borrowing ideas from robust optimization theory, the proposed formulations are made robust to moment estimation errors. A maximum margin classifier with specified false positive and false negative rates is derived. The key idea is to employ chance-constraints for each class which imply that the actual misclassification rates do not exceed the specified. The formulation is applied to the case of biased classification. The problems of large dataset classification and ordinal regression are addressed by deriving formulations which employ chance-constraints for clusters in training data rather than constraints for each data point. Since the number of clusters can be substantially smaller than the number of data points, the resulting formulation size and number of inequalities are very small. Hence the formulations scale well to large datasets. The scalable classification and OR formulations are extended to feature spaces and the kernelized duals turn out to be instances of SOCPs with a single cone constraint. Exploiting this speciality, fast iterative solvers which outperform generic SOCP solvers, are proposed. Compared to state-of-the-art learners, the proposed algorithms achieve a speed up as high as 10000 times, when the specialized SOCP solvers are employed. The proposed formulations involve second order moments of data and hence are susceptible to moment estimation errors. A generic way of making the formulations robust to such estimation errors is illustrated. Two novel confidence sets for moments are derived and it is shown that when either of the confidence sets are employed, the robust formulations also yield SOCPs.

The reliability analysis of plates and shells with respect to plastic collapse or to inadaptation is formulated on the basis of limit and shakedown theorems. The loading, the material strength and the shell thickness are considered as random variables. Based on a direct definition of the limit state function, the nonlinear problems may be efficiently solved by using the First and Second Order Reliability Methods (FORM/SORM). The sensitivity analyses in FORM/SORM can be based on the sensitivities of the deterministic shakedown problem. The problem of reliability of structural systems is also handled by the application of a special barrier technique which permits to find all the design points corresponding to all the failure modes. The direct plasticity approach reduces considerably the necessary knowledge of uncertain input data, computing costs and the numerical error. / Die Zuverlässigkeitsanalyse von Platten und Schalen in Bezug auf plastischen Kollaps oder Nicht-Anpassung wird mit den Traglast- und Einspielsätzen formuliert. Die Lasten, die Werkstofffestigkeit und die Schalendicke werden als Zufallsvariablen betrachtet. Auf der Grundlage einer direkten Definition der Grenzzustandsfunktion kann die Berechnung der Versagenswahrscheinlichkeit effektiv mit den Zuverlässigkeitsmethoden erster und zweiter Ordnung (FROM/SORM) gelöst werden. Die Sensitivitätsanalysen in FORM/SORM lassen sich auf der Basis der Sensitivitäten des deterministischen Einspielproblems berechnen. Die Schwierigkeiten bei der Ermittlung der Zuverlässigkeit von strukturellen Systemen werden durch Anwendung einer speziellen Barrieremethode behoben, die es erlaubt, alle Auslegungspunkte zu allen Versagensmoden zu finden. Die Anwendung direkter Plastizitätsmethoden führt zu einer beträchtlichen Verringerung der notwendigen Kenntnis der unsicheren Eingangsdaten, des Berechnungsaufwandes und der numerischen Fehler.

Σκοπός της παρούσας διδακτορικής διατριβής ήταν ο προσδιορισμός της υπερπολωσιμότητας δεύτερης τάξης διάφορων φουλλερενίων, παραγώγων φουλλερενίων και διθειολενικών συμπλόκων και η συσχέτιση αυτής με τη χημική δομή των υπό μελέτη υλικών. Για τη μελέτη των μη-γραμμικών οπτικών ιδιοτήτων των υλικών αυτών χρησιμοποιήθηκε η τεχνική Z-scan. Η μη-γραμμική τους απόκριση μελετήθηκε για παλμική διέγερση 35 ps και 8 ns, στα 532 και 1064 nm. Παράγοντες όπως ενίσχυση λόγω συντονισμού, μείωση της συμμετρίας, απεντοπισμός ηλεκτρονίων και μεταφορά φορτίου βρέθηκαν ότι επηρεάζουν σημαντικά τις μη-γραμμικές οπτικές ιδιότητες των συστημάτων αυτών. / The objective of this thesis was the determination of the second-order hyperpolarizability of some fullerenes, fullerene derivatives and dithiolene complexes and the understanding of the relation between the hyperpolarizability and the molecular structure. The non-linear optical properties of the above systems were investigated by the Z-scan technique. In particular, their non-linear optical response was studied under pulsed laser excitation having duration 35 ps and 8 ns, at 532 and 1064 nm. Several factors, like resonant enhancement, symmetry reduction, electron delocalization and charge transfer, were found to influence significantly the non-linear optical properties of these molecules.

Combinatorial problems are ubiquitous in our society and solving such problems efficiently is often crucial. One technique for solving combinatorial problems is constraint-based local search. Its compositional nature together with its efficiency on large problem instances have made this technique particularly attractive. In this thesis we contribute to simplifying the solving of combinatorial problems using constraint-based local search. To provide higher-level modelling options, we introduce set variables and set constraints in local search by extending relevant local search concepts. We also propose a general scheme to follow in order to define what we call natural and balanced constraint measures, and accordingly define such measures for over a dozen set constraints. However, defining such measures for a new constraint is time-consuming and error-prone. To relieve the user from this, we provide generic measures for any set constraint modelled in monadic existential second-order logic. We also theoretically relate these measures to our proposed general scheme, and discuss implementation issues such as incremental algorithms and their worst-case complexities. To enable higher-level search algorithms, we introduce constraint-directed neighbourhoods in local search by proposing new constraint primitives for representing such neighbourhoods. Based on a constraint, possibly modelled in monadic existential second-order logic, these primitives return neighbourhoods with moves that are known in advance to achieve a decrease (or preservation, or increase) of the constraint measures, without the need to iterate over any other moves. We also present a framework for constraint-based local search where one can model and solve combinatorial problems with set variables and set constraints, use any set constraint modelled in monadic existential second-order logic, as well as use constraint-directed neighbourhoods. Experimental results on three real-life problems show the usefulness in practice of our theoretical results: our running times are comparable to the current state-of-the-art approaches to solving the considered problems.

Les personnes ayant un trouble du spectre autistique (TSA) manifestent des particularités perceptives. En vision, des travaux influents chez les adultes ont mené à l’élaboration d’un modèle explicatif du fonctionnement perceptif autistique qui suggère que l’efficacité du traitement visuel varie en fonction de la complexité des réseaux neuronaux impliqués (Hypothèse spécifique à la complexité). Ainsi, lorsque plusieurs aires corticales sont recrutées pour traiter un stimulus complexe (e.g., modulations de texture; attributs de deuxième ordre), les adultes autistes démontrent une sensibilité diminuée. À l’inverse, lorsque le traitement repose principalement sur le cortex visuel primaire V1 (e.g., modulations locales de luminance; attributs de premier ordre), leur sensibilité est augmentée (matériel statique) ou intacte (matériel dynamique). Cette dissociation de performance est spécifique aux TSA et peut s’expliquer, entre autre, par une connectivité atypique au sein de leur cortex visuel. Les mécanismes neuronaux précis demeurent néanmoins méconnus. De plus, on ignore si cette signature perceptuelle est présente à l’enfance, information cruciale pour les théories perceptives de l’autisme. Le premier volet de cette thèse cherche à vérifier, à l’aide de la psychophysique et l’électrophysiologie, si la double dissociation de performance entre les attributs statiques de premier et deuxième ordre se retrouve également chez les enfants autistes d’âge scolaire. Le second volet vise à évaluer chez les enfants autistes l’intégrité des connexions visuelles descendantes impliquées dans le traitement des textures. À cet effet, une composante électrophysiologique reflétant principalement des processus de rétroaction corticale a été obtenue lors d’une tâche de ségrégation des textures. Les résultats comportementaux obtenus à l’étude 1 révèlent des seuils sensoriels similaires entre les enfants typiques et autistes à l’égard des stimuli définis par des variations de luminance et de texture. Quant aux données électrophysiologiques, il n’y a pas de différence de groupe en ce qui concerne le traitement cérébral associé aux stimuli définis par des variations de luminance. Cependant, contrairement aux enfants typiques, les enfants autistes ne démontrent pas une augmentation systématique d’activité cérébrale en réponse aux stimuli définis par des variations de texture pendant les fenêtres temporelles préférentiellement associées au traitement de deuxième ordre. Ces différences d’activation émergent après 200 ms et engagent les aires visuelles extrastriées des régions occipito-temporales et pariétales. Concernant la connectivité cérébrale, l’étude 2 indique que les connexions visuelles descendantes sont fortement asymétriques chez les enfants autistes, en défaveur de la région occipito-temporale droite. Ceci diffère des enfants typiques pour qui le signal électrophysiologique reflétant l’intégration visuo-corticale est similaire entre l’hémisphère gauche et droit du cerveau. En somme, en accord avec l’hypothèse spécifique à la complexité, la représentation corticale du traitement de deuxième ordre (texture) est atypiquement diminuée chez les enfants autistes, et un des mécanismes cérébraux impliqués est une altération des processus de rétroaction visuelle entre les aires visuelles de haut et bas niveau. En revanche, contrairement aux résultats obtenus chez les adultes, il n’y a aucun indice qui laisse suggérer la présence de mécanismes supérieurs pour le traitement de premier ordre (luminance) chez les enfants autistes. / Atypical perceptual information processing is commonly described in Autism Spectrum Disorders (ASD). In the visual modality, influential work with autistic adults suggests altered connectivity within specialized local networks defining the response properties of stimulus-driven mechanisms. This has led to the development of a hypothesis that stipulates that the efficiency of autistic visual perception is contingent on the complexity of the neural network involved (Complexity-specific hypothesis). When several cortical areas must communicate with each other (as in texture-defined perception, also called second-order), reduced sensitivity to visual input is observed in autistic individuals. In contrast, when visual processing predominately relies on the primary visual cortex V1 (as in luminance-defined perception, also called first-order), their sensitivity is either enhanced (stationary stimuli) or intact (moving stimuli). This dissociation in performance is unique to ASD and suggests atypical connectivity within their visual cortex. The precise type of neural alteration remains unknown, however. In addition, studies focusing on younger individuals are needed to define the developmental trajectories of perceptual abilities in autism. This issue is crucial for perceptual theories of ASD. The first experiment aims to investigate whether the dissociation regarding first- and second-order spatial vision is also present in school-aged children with autism. We combined the use of behavioural (psychophysics) and neuroimaging (visual evoked potentials: VEPs) methods. The second experiment was designed to assess the integrity of one type of neural connections that are known to be involved in texture processing: feedback processes from extrastriate areas towards lower hierarchical levels (V1). As such, we used a visual texture segregation task and isolated a texture-segregation specific VEP component that mainly reflects feedback modulation in the visual cortex. Behavioural measures from the first experiment do not reveal differences in visual thresholds between typically developing and autistic children for both luminance- and texture-defined stimuli. With respect to electrophysiology, there is no group difference in brain activity associated with luminance-defined stimuli. However, unlike typical children, autistic children do not reliably show reliable enhancements of brain activity in response to texture-defined stimuli during time-windows more closely associated with second-order processing. These differences emerge after 200 msec post-stimulation and mainly involve extrastriate areas located over occipito-temporal and parietal scalp areas. Regarding the second experiment, the texture-segregation specific VEP component is found to be greatly diminished over the right as compared to the left occipito-lateral cortex in autism, while it shows no hemispheric asymmetry in typically developing children. In summary, in line with the complexity-specific hypothesis, cortical representation of second-order attributes (texture) is atypically reduced in autistic children. This thesis further reveals that altered feedback from extrastriate visual areas to lower areas (V1) is one of the neuronal mechanisms involved in atypical texture processing. In contrast, contrary to the results obtained in adults with autism, first-order vision (luminance) is not found to be superior in autistic children.