Proposal of methodology for the modeling and control of manipulators

Industrial applications demand that robots operate in agreement with the position and orientation of their end effector. It is necessary to solve the kinematics inverse problem. This allows the displacement of the joints of the manipulator to be determined, to accomplish a given objective. Complete studies of dynamical control of joint robotics are also necessary. Initially, this article focuses on the implementation of numerical algorithms for the solution of the kinematics inverse problem and the modeling and simulation of dynamic systems. This is done using real time implementation. The modeling and simulation of dynamic systems are performed emphasizing off-line programming. In sequence, a complete study of the control strategies is carried out through the study of several elements of a robotic joint, such as: DC motor, inertia, and gearbox. Finally a trajectory generator, used as input for a generic group of joints, is developed and a proposal of the controller's implementation of joints, using EPLD development system, is presented.

Development of a process for the direct synthesis of hydrogen peroxide in a novel microstructured reactor

Microreactors have proven to be versatile tools for process intensification. Over recent decades, they have increasingly been used for product and process development in chemical industries. Enhanced heat and mass transfer in the reactors due to the extremely high surfacearea- to-volume ratio and interfacial area allow chemical processes to be operated at extreme conditions. Safety is improved by the small holdup volume of the reactors and effective control of pressure and temperature. Hydrogen peroxide is a powerful green oxidant that is used in a wide range of industries. Reduction and auto-oxidation of anthraquinones is currently the main process for hydrogen peroxide production. Direct synthesis is a green alternative and has potential for on-site production. However, there are two limitations: safety concerns because of the explosive gas mixture produced and low selectivity of the process. The aim of this thesis was to develop a process for direct synthesis of hydrogen peroxide utilizing microreactor technology. Experimental and numerical approaches were applied for development of the microreactor. Development of a novel microreactor was commenced by studying the hydrodynamics and mass transfer in prototype microreactor plates. The prototypes were designed and fabricated with the assistance of CFD modeling to optimize the shape and size of the microstructure. Empirical correlations for the mass transfer coefficient were derived. The pressure drop in micro T-mixers was investigated experimentally and numerically. Correlations describing the friction factor for different flow regimes were developed and predicted values were in good agreement with experimental results. Experimental studies were conducted to develop a highly active and selective catalyst with a proper form for the microreactor. Pd catalysts supported on activated carbon cloths were prepared by different treatments during the catalyst preparation. A variety of characterization methods were used for catalyst investigation. The surface chemistry of the support and the oxidation state of the metallic phase in the catalyst play important roles in catalyst activity and selectivity for the direct synthesis. The direct synthesis of hydrogen peroxide was investigated in a bench-scale continuous process using the novel microreactor developed. The microreactor was fabricated based on the hydrodynamic and mass transfer studies and provided a high interfacial area and high mass transfer coefficient. The catalysts were prepared under optimum treatment conditions. The direct synthesis was conducted at various conditions. The thesis represents a step towards a commercially viable direct synthesis. The focus is on the two main challenges: mitigating the safety problem by utilization of microprocess technology and improving the selectivity by catalyst development.

Taxonomy and distribution of the green algal genus Halimeda (Bryopsidales, Chlorophyta) in Brazil

Halimeda is a genus of calcified coenocytic green algae with a well known ecological importance in some tropical areas. Bleached calcified segments of Halimeda may accumulate in large deposits of economic potential as is the case in the northeastern coast of Brazil. In a survey of the genus in Brazil based on recent collections and examination of abundant material deposited on Brazilian herbaria we identified seven species: Halimeda cuneata Hering, H. discoidea Decaisne, H. gracilis Harvey ex J. Agardh, H. incrassata (Ellis) Lamouroux, H. opuntia (Linnaeus) Lamouroux, H. simulans Howe and H. tuna (Ellis & Solander) Lamouroux. These species are described in detail, with emphasis on diagnostic characters. Our study has shown that the shape and size of the utricula in surface view, under scanning electron microscopy, can be utilized to discriminate some species. Fertile specimens of Halimeda cuneata and H. discoidea are reported for the first time in the region. Data on vertical and geographical distribution are presented for each species and the southern limit of the genus in the western Atlantic was extended.

Production and characterization of lipid microparticles produced by spray cooling encapsulating a low molar mass hydrophilic compound

The objective of this research was to produce and characterize lipid particles (MpLs) that may be used as carriers of high amounts of hydrophilic core and evaluate the influence of the core amount on the performance of lipid microparticles. The MpLs were produced by spray cooling from solid and liquid lipid mixtures (stearic and oleic fatty acids and partly hydrogenated vegetable fat) containing glucose solution as core and soy lecithin as surfactant. The performance of MpLs was evaluated by means of the effective amount of encapsulated core, the core amount present on the surface of MpLs (superficial glucose) and the core release profile in aqueous solution. Morphological observations showed that MpLs presented spherical shape and a rugged and continuous surface, and an average diameter between 25 and 32 µm. The effective amount of encapsulated core was greater than 78% for all formulations evaluated. Larger amounts of superficial glucose were found in formulations in which more concentrated glucose solutions were used, regardless of the glucose lipid-solution ratio. The release results showed that core retention was significantly influenced by the glucose solution concentration, whereas release modulation was influenced by the glucose lipid-solution ratio.

Strategies for economic development in the Commonwealth Caribbean: a comparative study of the foreign economic policy strategies adopted by the Manley government in Jamaica and the Williams government in Trinidad and Tobago

This thesis compares the foreign economic poUcy dimension of the development strategies adopted by the governments of two Commonwealth caribbean countries: The Hardey government In Jamaica, and the· Williams government in Trlnidad and T ooago, The foreign economic policIes adopted by these governments appeared, on the surface~ to be markedly dissimilar. The Jamakan strategv on the one hand, emphasised self-reliance and national autonomy; and featured the espousal of radical oonaHgnment together with attempts to re-deftne the terms of the Islands externaa economIc relaUoos. The Trinidadian strategy 00 the other hand, featured Uberal externaUy-oriented growth poUctes, and close relatjoos with Western governments and financial institutions. Th1s study attempts to identify the explanatory factors that account for the apparent dlssimUarUy 1n the foreign economic policies of these two govemnents. The study is based on a comparison of how the structural bases of an underdeveloped ecooomYg and the foreign penetration and vulnerabUUy to external pressures asSOCiated wUh dependence, shape and influence foreign economic poUcy strategy. The framework views fore1gn ecooom1c strategy as an adaptive response on the part of the decision makers of a state to the coostralnts and opportunities provided by a particular situation. The · situat i 00' in this case being the events, conditions, structures and processes, associated wUh dependente and underdevelopment. The results indicate that the similarities and dissimHarities in the foreign economic policies of the governments of Jamaica and Trinidad were a reflecUon of the simHarities and dissimilarities in their respective situations. The conclusion derived suggests that If the foreign pol1cy field as an arena of choice, Is indeed one of opportunities and constraints for each and every state, then poHcy makers of smaU, weak, hlghW penetrated and vulnerable states enter thlS arena with constraints outweighing opportunities. This places effective limits 00 their decisional latitude and the range of policy options avaUable. Policy makers thus have to decide critical issues with few estabUshed precedents, in the face of domestic social and political cleavages, as wen as serious foreign pressures. This is a reflection not only of the trappings of dependence, but also of the Umned capabilities arising from the sman size of the state, and the Impact of the resource-gap In an underdeveloped economy. The Trinidadian strategy 1s UlustraUve of a development strategy made viable through a combination of a fortuitous circumstance, a confluence of the interests of influential groups» and accurate perception on the part of poUcy makers. These factors enabled policy makers to minimise some of the constraints of dependence. The faUure of Manlets strategy on the other hand, 15 iHustraUve of the problems involved tn the adoption of poUcles that work against the interest of internal and external political and economic forces. It is also tUustraUve of the consequences of the faUure 00 the part of policy makers to clarify goals, and to reconcile the values of rapid economic growth with increased self-reliance and national autonomy. These values tend to be mutuany Incompatible given the existing patterns of relations in the jnternational economy.

Mirroring Enzymes: The Role of H-Bonding In HQuin-BAM Catalyzed Asymmetric Aza-Henry Reactions: A DFT Study into the Reactivity, Mechanism, and Origins of Selectivity

The exact mechanistic understanding of various organocatalytic systems in asymmetric reactions such as Henry and aza-Henry transformations is important for developing and designing new synthetic organocatalysts. The focus of this dissertation will be on the use of density functional theory (DFT) for studying the asymmetric aza-Henry reaction. The first part of the thesis is a detailed mechanistic investigation of a poorly understood chiral bis(amidine) (BAM) Brønsted acid catalyzed aza-Henry reaction between nitromethane and N-Boc phenylaldimine. The catalyst, in addition to acting as a Brønsted base, serves to simultaneously activate both the electrophile and the nucleophile through dual H-bonding during C-C bond formation and is thus essential for both reaction rate and selectivity. Analysis of the H-bonding interactions revealed that there was a strong preference for the formation of a homonuclear positive charge-assisted H-bond, which in turn governed the relative orientation of substrate binding. Attracted by this well-defined mechanistic investigation, the other important aspect of my PhD research addressed a detailed theoretical analysis accounting for the observed selectivity in diastereoselective versions of this reaction. A detailed inspection of the stereodetermining C-C bond forming transition states for monoalkylated nitronate addition to a range of electronically different aldimines, revealed that the origins of stereoselectivity were controlled by a delicate balance of different factors such as steric, orbital interactions, and the extent of distortion in the catalyst and substrates. The structural analysis of different substituted transition states established an interesting dependency on matching the shape and size of the catalyst (host molecule) and substrates (guest molecules) upon binding, both being key factors governing selectivity, in essence, offering an analogy to positive cooperative binding effect of catalytic enzymes and substrates in Nature. In addition, both intra-molecular (intra-host) and inter-molecular (host-guest, guest-guest) stabilizing interactions play a key role to the high π-facial selectivity. The application of dispersion-corrected functionals (i.e., ωB97X-D and B3LYP-D3) was essential for accurately modeling these stabilizing interactions, indicating the importance of dispersion effects in enantioselectivity. As a brief prelude to more extensive future studies, the influence of a triflate counterion on both reactivity and selectivity in this reaction was also addressed.

Modélisation procédurale par composants

Le réalisme des images en infographie exige de créer des objets (ou des scènes) de plus en plus complexes, ce qui entraîne des coûts considérables. La modélisation procédurale peut aider à automatiser le processus de création, à simplifier le processus de modification ou à générer de multiples variantes d'une instance d'objet. Cependant même si plusieurs méthodes procédurales existent, aucune méthode unique permet de créer tous les types d'objets complexes, dont en particulier un édifice complet. Les travaux réalisés dans le cadre de cette thèse proposent deux solutions au problème de la modélisation procédurale: une solution au niveau de la géométrie de base, et l’autre sous forme d'un système général adapté à la modélisation des objets complexes. Premièrement, nous présentons le bloc, une nouvelle primitive de modélisation simple et générale, basée sur une forme cubique généralisée. Les blocs sont disposés et connectés entre eux pour constituer la forme de base des objets, à partir de laquelle est extrait un maillage de contrôle pouvant produire des arêtes lisses et vives. La nature volumétrique des blocs permet une spécification simple de la topologie, ainsi que le support des opérations de CSG entre les blocs. La paramétrisation de la surface, héritée des faces des blocs, fournit un soutien pour les textures et les fonctions de déplacements afin d'appliquer des détails de surface. Une variété d'exemples illustrent la généralité des blocs dans des contextes de modélisation à la fois interactive et procédurale. Deuxièmement, nous présentons un nouveau système de modélisation procédurale qui unifie diverses techniques dans un cadre commun. Notre système repose sur le concept de composants pour définir spatialement et sémantiquement divers éléments. À travers une série de déclarations successives exécutées sur un sous-ensemble de composants obtenus à l'aide de requêtes, nous créons un arbre de composants définissant ultimement un objet dont la géométrie est générée à l'aide des blocs. Nous avons appliqué notre concept de modélisation par composants à la génération d'édifices complets, avec intérieurs et extérieurs cohérents. Ce nouveau système s'avère général et bien adapté pour le partionnement des espaces, l'insertion d'ouvertures (portes et fenêtres), l'intégration d'escaliers, la décoration de façades et de murs, l'agencement de meubles, et diverses autres opérations nécessaires lors de la construction d'un édifice complet.

Spectrum simulation of rough and nanostructured targets from their 2D and 3D image by Monte Carlo methods

Corteo is a program that implements Monte Carlo (MC) method to simulate ion beam analysis (IBA) spectra of several techniques by following the ions trajectory until a sufficiently large fraction of them reach the detector to generate a spectrum. Hence, it fully accounts for effects such as multiple scattering (MS). Here, a version of Corteo is presented where the target can be a 2D or 3D image. This image can be derived from micrographs where the different compounds are identified, therefore bringing extra information into the solution of an IBA spectrum, and potentially significantly constraining the solution. The image intrinsically includes many details such as the actual surface or interfacial roughness, or actual nanostructures shape and distribution. This can for example lead to the unambiguous identification of structures stoichiometry in a layer, or at least to better constraints on their composition. Because MC computes in details the trajectory of the ions, it simulates accurately many of its aspects such as ions coming back into the target after leaving it (re-entry), as well as going through a variety of nanostructures shapes and orientations. We show how, for example, as the ions angle of incidence becomes shallower than the inclination distribution of a rough surface, this process tends to make the effective roughness smaller in a comparable 1D simulation (i.e. narrower thickness distribution in a comparable slab simulation). Also, in ordered nanostructures, target re-entry can lead to replications of a peak in a spectrum. In addition, bitmap description of the target can be used to simulate depth profiles such as those resulting from ion implantation, diffusion, and intermixing. Other improvements to Corteo include the possibility to interpolate the cross-section in angle-energy tables, and the generation of energy-depth maps.

Surface electron properties and catalytic activity of cerium-zirconium mixed oxides

The electron donating properties, surface acidity/ basicity and catalytic activity of cerium - zirconium mixed oxides at various compositions have been reported at an activation temperature of 500 degree C. The catalytic activity for the esterification of acetic acid with n-butanol has heen correlated with electron donating properties and surface acidity/basicity of the oxides.

Surface electron properties and catalytic activity of Sr doped lanthana

The electron donating properties, surface acidity/basicity and catalytic activity of lanthana for various dopant concentrations of strontium are reported at two activation temperatures. The catalytic activity has been correlated with electron donating properties and surface acidity/basicity of the oxide.

Influence of substrate topography on the growth and magnetic properties of obliquely deposited amorphous nanocolumns of Fe–Ni

We investigated the influence of substrate surface roughness on the structural and magnetic properties of obliquely deposited amorphous nanocolumns of Fe–Ni. Experiments showed that the surface roughness of the substrate greatly determines the morphology of the columnar structures and this in turn has a profound influence on the magnetic properties. Nucleation of Fe–Ni nanocolumns on a smooth silicon substrate was at random, while that on a rough glass substrate was defined by the irregularities on the substrate surface. It has been found that magnetic interaction between the nanocolumns prepared on a silicon substrate was due to their small inter-column separation. Well separated nanocolumns on a glass substrate resulted in exchange isolated magnetic domains. The size, shape and the distribution of nanocolumns can be tailored by appropriately choosing the surface roughness of the substrate. This will find potential applications in thin film magnetism.

Swift heavy ion induced surface and microstructural evolution in metallic glass thin films

Swift heavy ion induced changes in microstructure and surface morphology of vapor deposited Fe–Ni based metallic glass thin films have been investigated by using atomic force microscopy, X-ray diffraction and transmission electron microscopy. Ion beam irradiation was carried out at room temperature with 103 MeV Au9+ beam with fluences ranging from 3 1011 to 3 1013 ions/cm2. The atomic force microscopy images were subjected to power spectral density analysis and roughness analysis using an image analysis software. Clusters were found in the image of as-deposited samples, which indicates that the film growth is dominated by the island growth mode. As-deposited films were amorphous as evidenced from X-ray diffraction; however, high resolution transmission electron microscopy measurements revealed a short range atomic order in the samples with crystallites of size around 3 nm embedded in an amorphous matrix. X-ray diffraction pattern of the as-deposited films after irradiation does not show any appreciable changes, indicating that the passage of swift heavy ions stabilizes the short range atomic ordering, or even creates further amorphization. The crystallinity of the as-deposited Fe–Ni based films was improved by thermal annealing, and diffraction results indicated that ion beam irradiation on annealed samples results in grain fragmentation. On bombarding annealed films, the surface roughness of the films decreased initially, then, at higher fluences it increased. The observed change in surface morphology of the irradiated films is attributed to the interplay between ion induced sputtering, volume diffusion and surface diffusion

Performance Assessment of Sandwich Structures with Debonds and Dents

A sandwich construction is a special form of the laminated composite consisting of light weight core, sandwiched between two stiff thin face sheets. Due to high stiffness to weight ratio, sandwich construction is widely adopted in aerospace industries. As a process dependent bonded structure, the most severe defects associated with sandwich construction are debond (skin core bond failure) and dent (locally deformed skin associated with core crushing). Reasons for debond may be attributed to initial manufacturing flaws or in service loads and dent can be caused by tool drops or impacts by foreign objects. This paper presents an evaluation on the performance of honeycomb sandwich cantilever beam with the presence of debond or dent, using layered finite element models. Dent is idealized by accounting core crushing in the core thickness along with the eccentricity of the skin. Debond is idealized using multilaminate modeling at debond location with contact element between the laminates. Vibration and buckling behavior of metallic honeycomb sandwich beam with and without damage are carried out. Buckling load factor, natural frequency, mode shape and modal strain energy are evaluated using finite element package ANSYS 13.0. Study shows that debond affect the performance of the structure more severely than dent. Reduction in the fundamental frequencies due to the presence of dent or debond is not significant for the case considered. But the debond reduces the buckling load factor significantly. Dent of size 8-20% of core thickness shows 13% reduction in buckling load capacity of the sandwich column. But debond of the same size reduced the buckling load capacity by about 90%. This underscores the importance of detecting these damages in the initiation level itself to avoid catastrophic failures. Influence of the damages on fundamental frequencies, mode shape and modal strain energy are examined. Effectiveness of these parameters as a damage detection tool for sandwich structure is also assessed

Low-Cost Micromechanically Tunable Optical Devices: Strained Resonator Engineering, Technological Implementation and Characterization

The rapid growth of the optical communication branches and the enormous demand for more bandwidth require novel networks such as dense wavelength division multiplexing (DWDM). These networks enable higher bitrate transmission using the existing optical fibers. Micromechanically tunable optical microcavity devices like VCSELs, Fabry-Pérot filters and photodetectors are core components of these novel DWDM systems. Several air-gap based tunable devices were successfully implemented in the last years. Even though these concepts are very promising, two main disadvantages are still remaining. On the one hand, the high fabrication and integration cost and on the other hand the undesired adverse buckling of the suspended membranes. This thesis addresses these two problems and consists of two main parts: • PECVD dielectric material investigation and stress control resulting in membranes shape engineering. • Implementation and characterization of novel tunable optical devices with tailored shapes of the suspended membranes. For this purposes, low-cost PECVD technology is investigated and developed in detail. The macro- and microstress of silicon nitride and silicon dioxide are controlled over a wide range. Furthermore, the effect of stress on the optical and mechanical properties of the suspended membranes and on the microcavities is evaluated. Various membrane shapes (concave, convex and planar) with several radii of curvature are fabricated. Using this resonator shape engineering, microcavity devices such as non tunable and tunable Fabry-Pérot filters, VCSELs and PIN photodetectors are succesfully implemented. The fabricated Fabry-Pérot filters cover a spectral range of over 200nm and show resonance linewidths down to 1.5nm. By varying the stress distribution across the vertical direction within a DBR, the shape and the radius of curvature of the top membrane are explicitely tailored. By adjusting the incoming light beam waist to the curvature, the fundamental resonant mode is supported and the higher order ones are suppressed. For instance, a tunable VCSEL with 26 nm tuning range, 400µW maximal output power, 47nm free spectral range and over 57dB side mode suppresion ratio (SMSR) is demonstrated. Other technologies, such as introducing light emitting organic materials in microcavities are also investigated.