Surface studies of limestones and dolostones : characterisation using various techniques and batch dissolution experiments with hydrochloric acid solutions

In this thesis, stepwise titration with hydrochloric acid was used to obtain chemical reactivities and dissolution rates of ground limestones and dolostones of varying geological backgrounds (sedimentary, metamorphic or magmatic). Two different ways of conducting the calculations were used: 1) a first order mathematical model was used to calculate extrapolated initial reactivities (and dissolution rates) at pH 4, and 2) a second order mathematical model was used to acquire integrated mean specific chemical reaction constants (and dissolution rates) at pH 5. The calculations of the reactivities and dissolution rates were based on rate of change of pH and particle size distributions of the sample powders obtained by laser diffraction. The initial dissolution rates at pH 4 were repeatedly higher than previously reported literature values, whereas the dissolution rates at pH 5 were consistent with former observations. Reactivities and dissolution rates varied substantially for dolostones, whereas for limestones and calcareous rocks, the variation can be primarily explained by relatively large sample standard deviations. A list of the dolostone samples in a decreasing order of initial reactivity at pH 4 is: 1) metamorphic dolostones with calcite/dolomite ratio higher than about 6% 2) sedimentary dolostones without calcite 3) metamorphic dolostones with calcite/dolomite ratio lower than about 6% The reactivities and dissolution rates were accompanied by a wide range of experimental techniques to characterise the samples, to reveal how different rocks changed during the dissolution process, and to find out which factors had an influence on their chemical reactivities. An emphasis was put on chemical and morphological changes taking place at the surfaces of the particles via X-ray Photoelectron Spectroscopy (XPS) and Scanning Electron Microscopy (SEM). Supporting chemical information was obtained with X-Ray Fluorescence (XRF) measurements of the samples, and Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) and Inductively Coupled Plasma-Optical Emission Spectrometry (ICP-OES) measurements of the solutions used in the reactivity experiments. Information on mineral (modal) compositions and their occurrence was provided by X-Ray Diffraction (XRD), Energy Dispersive X-ray analysis (EDX) and studying thin sections with a petrographic microscope. BET (Brunauer, Emmet, Teller) surface areas were determined from nitrogen physisorption data. Factors increasing chemical reactivity of dolostones and calcareous rocks were found to be sedimentary origin, higher calcite concentration and smaller quartz concentration. Also, it is assumed that finer grain size and larger BET surface areas increase the reactivity although no certain correlation was found in this thesis. Atomic concentrations did not correlate with the reactivities. Sedimentary dolostones, unlike metamorphic ones, were found to have porous surface structures after dissolution. In addition, conventional (XPS) and synchrotron based (HRXPS) X-ray Photoelectron Spectroscopy were used to study bonding environments on calcite and dolomite surfaces. Both samples are insulators, which is why neutralisation measures such as electron flood gun and a conductive mask were used. Surface core level shifts of 0.7 ± 0.1 eV for Ca 2p spectrum of calcite and 0.75 ± 0.05 eV for Mg 2p and Ca 3s spectra of dolomite were obtained. Some satellite features of Ca 2p, C 1s and O 1s spectra have been suggested to be bulk plasmons. The origin of carbide bonds was suggested to be beam assisted interaction with hydrocarbons found on the surface. The results presented in this thesis are of particular importance for choosing raw materials for wet Flue Gas Desulphurisation (FGD) and construction industry. Wet FGD benefits from high reactivity, whereas construction industry can take advantage of slow reactivity of carbonate rocks often used in the facades of fine buildings. Information on chemical bonding environments may help to create more accurate models for water-rock interactions of carbonates.

Comparaison de l’ubiquitylation de différentes protéines à domaine SH3 impliquées dans l’endocytose suite à leur interaction avec la ligase de l’ubiquitine Itch

Itch est la seule ligase de l'ubiquitine de type C2-WW-HECT capable d'interagir avec les protéines à domaine SH3. Ce domaine est particulièrement représenté parmi les protéines régulatrices de l'endocytose. Les travaux présentés ici visaient à examiner la capacité d'Itch à interagir avec plusieurs protéines endocytiques. Nous avons utilisé la technique du BRET (Bioluminescence Resonance Energy Transfer) pour examiner quelques protéines candidates. Nous avons ensuite confirmé les résultats obtenus par BRET avec des tests d'interaction in vitro, puis déterminé la capacité d'Itch à ubiquityler les protéines liées via leurs domaines SH3. Nous avons ainsi découvert deux nouveaux partenaires d'interaction et substrats d'Itch parmi les protéines endocytiques, amphyphisine et pacsine. De plus, Itch interagit avec les domaines SH3 isolés d'intersectine, mais pas avec la protéine complète, suggérant que cette dernière n'est pas un substrat d'Itch. Itch est donc bien positionnée pour exercer un rôle régulateur de l'endocytose en ubiquitylant ses substrats.

Development of active microwave imaging techniques for applications in mammography

Breast cancer is the most common non - skin malignancy in women and a leading cause of female morality. A potentially important strategy for reducing this menace is the detection at an early stage . The invention of non-invasive and non-ionizing microwave technique, to reveal the internal structure of biological objects was a break through in the field of medical diagnostics. Electrical properties of biological tissues and their interaction with electromagmetic waves have direct impact on human life. This thesis focuses on theoretical and experimental investigations of active microwave imaging techniques for breast cancer detection.

Techniques for Enhancing Wind Energy Generation - A CFD Based Multibody Dynamics Approach in Horizontal Axis Wind Turbines

Wind energy has emerged as a major sustainable source of energy.The efficiency of wind power generation by wind mills has improved a lot during the last three decades.There is still further scope for maximising the conversion of wind energy into mechanical energy.In this context,the wind turbine rotor dynamics has great significance.The present work aims at a comprehensive study of the Horizontal Axis Wind Turbine (HAWT) aerodynamics by numerically solving the fluid dynamic equations with the help of a finite-volume Navier-Stokes CFD solver.As a more general goal,the study aims at providing the capabilities of modern numerical techniques for the complex fluid dynamic problems of HAWT.The main purpose is hence to maximize the physics of power extraction by wind turbines.This research demonstrates the potential of an incompressible Navier-Stokes CFD method for the aerodynamic power performance analysis of horizontal axis wind turbine.The National Renewable Energy Laboratory USA-NREL (Technical Report NREL/Cp-500-28589) had carried out an experimental work aimed at the real time performance prediction of horizontal axis wind turbine.In addition to a comparison between the results reported by NREL made and CFD simulations,comparisons are made for the local flow angle at several stations ahead of the wind turbine blades.The comparison has shown that fairly good predictions can be made for pressure distribution and torque.Subsequently, the wind-field effects on the blade aerodynamics,as well as the blade/tower interaction,were investigated.The selected case corresponded to a 12.5 m/s up-wind HAWT at zero degree of yaw angle and a rotational speed of 25 rpm.The results obtained suggest that the present can cope well with the flows encountered around wind turbines.The areodynamic performance of the turbine and the flow details near and off the turbine blades and tower can be analysed using theses results.The aerodynamic performance of airfoils differs from one another.The performance mainly depends on co-efficient of performnace,co-efficient of lift,co-efficient of drag, velocity of fluid and angle of attack.This study shows that the velocity is not constant for all angles of attack of different airfoils.The performance parameters are calculated analytically and are compared with the standardized performance tests.For different angles of ,the velocity stall is determined for the better performance of a system with respect to velocity.The research addresses the effect of surface roughness factor on the blade surface at various sections.The numerical results were found to be in agreement with the experimental data.A relative advantage of the theoretical aerofoil design method is that it allows many different concepts to be explored economically.Such efforts are generally impractical in wind tunnels because of time and money constraints.Thus, the need for a theoretical aerofoil design method is threefold:first for the design of aerofoil that fall outside the range of applicability of existing calalogs:second,for the design of aerofoil that more exactly match the requirements of the intended application:and third,for the economic exploration of many aerofoil concepts.From the results obtained for the different aerofoils,the velocity is not constant for all angles of attack.The results obtained for the aerofoil mainly depend on angle of attack and velocity.The vortex generator technique was meticulously studies with the formulation of the specification for the right angle shaped vortex generators-VG.The results were validated in accordance with the primary analysis phase.The results were found to be in good agreement with the power curve.The introduction of correct size VGs at appropriate locations over the blades of the selected HAWT was found to increase the power generation by about 4%

Teaching an Old Robot New Tricks: Learning Novel Tasks via Interaction with People and Things

As AI has begun to reach out beyond its symbolic, objectivist roots into the embodied, experientialist realm, many projects are exploring different aspects of creating machines which interact with and respond to the world as humans do. Techniques for visual processing, object recognition, emotional response, gesture production and recognition, etc., are necessary components of a complete humanoid robot. However, most projects invariably concentrate on developing a few of these individual components, neglecting the issue of how all of these pieces would eventually fit together. The focus of the work in this dissertation is on creating a framework into which such specific competencies can be embedded, in a way that they can interact with each other and build layers of new functionality. To be of any practical value, such a framework must satisfy the real-world constraints of functioning in real-time with noisy sensors and actuators. The humanoid robot Cog provides an unapologetically adequate platform from which to take on such a challenge. This work makes three contributions to embodied AI. First, it offers a general-purpose architecture for developing behavior-based systems distributed over networks of PC's. Second, it provides a motor-control system that simulates several biological features which impact the development of motor behavior. Third, it develops a framework for a system which enables a robot to learn new behaviors via interacting with itself and the outside world. A few basic functional modules are built into this framework, enough to demonstrate the robot learning some very simple behaviors taught by a human trainer. A primary motivation for this project is the notion that it is practically impossible to build an "intelligent" machine unless it is designed partly to build itself. This work is a proof-of-concept of such an approach to integrating multiple perceptual and motor systems into a complete learning agent.

Gradient-based reinforcement learning techniques for underwater robotics behavior learning

Darrerament, l'interès pel desenvolupament d'aplicacions amb robots submarins autònoms (AUV) ha crescut de forma considerable. Els AUVs són atractius gràcies al seu tamany i el fet que no necessiten un operador humà per pilotar-los. Tot i això, és impossible comparar, en termes d'eficiència i flexibilitat, l'habilitat d'un pilot humà amb les escasses capacitats operatives que ofereixen els AUVs actuals. L'utilització de AUVs per cobrir grans àrees implica resoldre problemes complexos, especialment si es desitja que el nostre robot reaccioni en temps real a canvis sobtats en les condicions de treball. Per aquestes raons, el desenvolupament de sistemes de control autònom amb l'objectiu de millorar aquestes capacitats ha esdevingut una prioritat. Aquesta tesi tracta sobre el problema de la presa de decisions utilizant AUVs. El treball presentat es centra en l'estudi, disseny i aplicació de comportaments per a AUVs utilitzant tècniques d'aprenentatge per reforç (RL). La contribució principal d'aquesta tesi consisteix en l'aplicació de diverses tècniques de RL per tal de millorar l'autonomia dels robots submarins, amb l'objectiu final de demostrar la viabilitat d'aquests algoritmes per aprendre tasques submarines autònomes en temps real. En RL, el robot intenta maximitzar un reforç escalar obtingut com a conseqüència de la seva interacció amb l'entorn. L'objectiu és trobar una política òptima que relaciona tots els estats possibles amb les accions a executar per a cada estat que maximitzen la suma de reforços totals. Així, aquesta tesi investiga principalment dues tipologies d'algoritmes basats en RL: mètodes basats en funcions de valor (VF) i mètodes basats en el gradient (PG). Els resultats experimentals finals mostren el robot submarí Ictineu en una tasca autònoma real de seguiment de cables submarins. Per portar-la a terme, s'ha dissenyat un algoritme anomenat mètode d'Actor i Crític (AC), fruit de la fusió de mètodes VF amb tècniques de PG.

Engineering Pt in ceria for a maximum metal-support interaction in catalysis

Conventional supported metal catalysts are metal nanoparticles deposited on high surface area oxide supports with a poorly defined metal−support interface. Typically, the traditionally prepared Pt/ceria catalyzes both methanation (H2/CO to CH4) and water−gas shift (CO/H2O to CO2/H2) reactions. By using simple nanochemistry techniques, we show for the first time that Pt or PtAu metal can be created inside each CeO2 particle with tailored dimensions. The encapsulated metal is shown to interact with the thin CeO2 overlayer in each single particle in an optimum geometry to create a unique interface, giving high activity and excellent selectivity for the water−gas shift reaction, but is totally inert for methanation. Thus, this work clearly demonstrates the significance of nanoengineering of a single catalyst particle by a bottom-up construction approach in modern catalyst design which could enable exploitation of catalyst site differentiation, leading to new catalytic properties.

An analysis on the performance of the forward and return interaction channels in DVB-RCS

The next generation consumer level interactive services require reliable and constant communication for both mobile and static users. The Digital Video Broadcasting ( DVB) group has exploited the rapidly increasing satellite technology for the provision of interactive services and launched a standard called Digital Video Broadcast through Return Channel Satellite (DYB-RCS). DVB-RCS relies on DVB-Satellite (DVB-S) for the provision of forward channel. The Digital Signal processing (DSP) implemented in the satellite channel adapter block of these standards use powerful channel coding and modulation techniques. The investigation is concentrated towards the Forward Error Correction (FEC) of the satellite channel adapter block, which will help in determining, how the technology copes with the varying channel conditions and user requirements(1).

A comparison of space weather analysis techniques used to predict the arrival of the Earth-directed CME and its shockwave launched on 8 April 2010

The Earth-directed coronal mass ejection (CME) of 8 April 2010 provided an opportunity for space weather predictions from both established and developmental techniques to be made from near–real time data received from the SOHO and STEREO spacecraft; the STEREO spacecraft provide a unique view of Earth-directed events from outside the Sun-Earth line. Although the near–real time data transmitted by the STEREO Space Weather Beacon are significantly poorer in quality than the subsequently downlinked science data, the use of these data has the advantage that near–real time analysis is possible, allowing actual forecasts to be made. The fact that such forecasts cannot be biased by any prior knowledge of the actual arrival time at Earth provides an opportunity for an unbiased comparison between several established and developmental forecasting techniques. We conclude that for forecasts based on the STEREO coronagraph data, it is important to take account of the subsequent acceleration/deceleration of each CME through interaction with the solar wind, while predictions based on measurements of CMEs made by the STEREO Heliospheric Imagers would benefit from higher temporal and spatial resolution. Space weather forecasting tools must work with near–real time data; such data, when provided by science missions, is usually highly compressed and/or reduced in temporal/spatial resolution and may also have significant gaps in coverage, making such forecasts more challenging.

The study of chiral adsorption systems using synchrotron- based structural and spectroscopic techniques: stereospecific adsorption of serine on Au-modified chiral Cu{531} surfaces

We apply modern synchrotron-based structural techniques to the study of serine adsorbed on the pure andAumodified intrinsically chiral Cu{531} surface. XPS and NEXAFS data in combination with DFT show that on the pure surface both enantiomers adsorb in l4 geometries (with de-protonated b-OH groups) at low coverage and in l3 geometries at saturation coverage. Significantly larger enantiomeric differences are seen for the l4 geometries, which involve substrate bonds of three side groups of the chiral center, i.e. a three-point interaction. The l3 adsorption geometry, where only the carboxylate and amino groups form substrate bonds, leads to smaller but still significant enantiomeric differences, both in geometry and the decomposition behavior. When Cu{531} is modified by the deposition of 1 and 2ML Au the orientations of serine at saturation coverage are significantly different from those on the clean surface. In all cases, however, a l3 bond coordination is found at saturation involving different numbers of Au atoms, which leads to relatively small enantiomeric differences.

Dimer formation by symbiotic donor–acceptor interaction between two molecules of a specially designed dioxomolybdenum(VI) complex containing both donor and acceptor centers – A structural, spectroscopic and DFT study

This work presents a model study for the formation of a dimeric dioxomolybdenum(VI) complex [MoO2L]2, generated by simultaneous satisfaction of acceptor and donor character existing in the corresponding monomeric Mo(VI) complex MoO2L. This mononuclear complex is specially designed to contain a coordinatively unsaturated Mo(VI) acceptor centre and a free donor group, (e.g. –NH2 group) strategically placed in the ligand skeleton [H2L = 2-hydroxyacetophenonehydrazone of 2-aminobenzoylhydrazine]. Apart from the dimer [MoO2L]2, complexes of the type MoO2L·B (where B = CH3OH, γ-picoline and imidazole) are also reported. All the complexes are characterized by elemental analysis, spectroscopic (UV–Vis, IR, 1H NMR) techniques and cyclic voltammetry. Single crystal X-ray structures of [MoO2L]2 (1), MoO2L·CH3OH (2), and MoO2L.(γ-pic) (3) have been determined and discussed. DFT calculation on these complexes corroborates experimental data and provides clue for the facile formation of this type of dimer not reported previously. The process of dimer formation may also be viewed as an interaction between two molecules of a specially designed complex acting as a monodentate ligand. This work is expected to open up a new field of design and synthesis of dimeric complexes through the process of symbiotic donor–acceptor (acid–base) interaction between two molecules of a specially designed monomer.

An investigation into the impact of using various techniques to estimate Arctic surface air temperature anomalies

Time series of global and regional mean Surface Air Temperature (SAT) anomalies are a common metric used to estimate recent climate change. Various techniques can be used to create these time series from meteorological station data. The degree of difference arising from using five different techniques, based on existing temperature anomaly dataset techniques, to estimate Arctic SAT anomalies over land and sea ice were investigated using reanalysis data as a testbed. Techniques which interpolated anomalies were found to result in smaller errors than non-interpolating techniques relative to the reanalysis reference. Kriging techniques provided the smallest errors in estimates of Arctic anomalies and Simple Kriging was often the best kriging method in this study, especially over sea ice. A linear interpolation technique had, on average, Root Mean Square Errors (RMSEs) up to 0.55 K larger than the two kriging techniques tested. Non-interpolating techniques provided the least representative anomaly estimates. Nonetheless, they serve as useful checks for confirming whether estimates from interpolating techniques are reasonable. The interaction of meteorological station coverage with estimation techniques between 1850 and 2011 was simulated using an ensemble dataset comprising repeated individual years (1979-2011). All techniques were found to have larger RMSEs for earlier station coverages. This supports calls for increased data sharing and data rescue, especially in sparsely observed regions such as the Arctic.

Design patterns for promoting peer interaction in discussion forums in MOOCs

Design patterns are a way of sharing evidence-based solutions to educational design problems. The design patterns presented in this paper were produced through a series of workshops, which aimed to identify Massive Open Online Course (MOOC) design principles from workshop participants’ experiences of designing, teaching and learning on these courses. MOOCs present a challenge for the existing pedagogy of online learning, particularly as it relates to promoting peer interaction and discussion. MOOC cohort sizes, participation patterns and diversity of learners mean that discussions can remain superficial, become difficult to navigate, or never develop beyond isolated posts. In addition, MOOC platforms may not provide sufficient tools to support moderation. This paper draws on four case studies of designing and teaching on a range of MOOCs presenting seven design narratives relating to the experience in these MOOCs. Evidence presented in the narratives is abstracted in the form of three design patterns created through a collaborative process using techniques similar to those used in collective autoethnography. The patterns: “Special Interest Discussions”, “Celebrity Touch” and “Look and Engage”, draw together shared lessons and present possible solutions to the problem of creating, managing and facilitating meaningful discussion in MOOCs through the careful use of staged learning activities and facilitation strategies.

Human resource allocation management in multiple projects using sociometric techniques

This article describes a new application of key psychological concepts in the area of Sociometry for the selection of workers within organizations in which projects are developed. The project manager can use a new procedure to determine which individuals should be chosen from a given pool of resources and how to combine them into one or several simultaneous groups/projects in order to assure the highest possible overall work efficiency from the standpoint of social interaction. The optimization process was carried out by means of matrix calculations performed using a computer or even manually, and based on a number of new ratios generated ad-hoc and composed on the basis of indices frequently used in Sociometry.

On the interaction of the anthraquinone barbaloin with negatively charged DMPG bilayers

Barbaloin is a bioactive glycosilated 1,8-dihydroxyanthraquinone present in several exudates from plants, Such as Aloe vera, which are used for cosmetic or food purposes. It has been shown that barbaloin interacts with DMPG (dimyristoylphosphatidylglycerol) model membranes, altering the bilayer structure (Alves, D. S.; Perez-Fons, L.; Estepa, A.; Micol, V. Biochem. Pharm. 2004, 68, 549). Considering that ESR (electron spin resonance) of spin labels is one of the best techniques to monitor structural properties at the molecular level, the alterations caused by the anthraquinone barbaloin on phospholipid bilayers will be discussed here via the ESR signal of phospholipid spin probes intercalated into the membranes. In DMPG at high ionic strength (10 mM Hepes pH 7.4 + 100 mM NaCl), a system that presents a gel-fluid transition around 23 degrees C, 20 mol % barbaloin turns the gel phase more rigid, does not alter much the fluid phase packing, but makes the lipid thermal transition less sharp. However, in a low-salt DMPG dispersion (10 mM Hepes pH 7.4 + 2 mM NaCl), which presents a rather complex gel-fluid thermal transition (Lamy-Freund, M. T.; Riske, K. A. Chem. Phys. Lipids 2003, 122, 19), barbaloin strongly affects bilayer structural properties, both in the gel and fluid phases, extending the transition region to much higher temperature values. The position of barbaloin in DMPG bilayers will be discussed on the basis of ESR results, in parallel with data from sample viscosity, DSC (differential scanning calorimetry), and SAXS (small-angle X-ray scattering).