Le but de cette thèse est d'étudier d'une façon expérimentale et théorique le comportement synchrone d'un groupe d'oscillateurs contrôlés par la lumière (LCOs). Ces LCOs sont très simples du point de vue électronique et ont la propriété d'imiter le comportement des lucioles puisqu'ils interagissent par des impulsions de lumière. En même temps, les LCOs sont une bonne approche pour étudier d'autres systèmes qui agissent comme des oscillateurs d'intégration et de tir car un LCO est un oscillateur de relaxation à deux échelles de temps :un long processus de charge alterné avec un très court processus de décharge. Une série d'expériences a été menée pour pouvoir comprendre le processus de synchronisation des LCOs. Nous avons trouvé que l'acquisition de la synchronisation est due aux effets de la perturbation à savoir: le raccourcissement de la charge et l'allongement de la décharge. Les mesures expérimentales ainsi que la physique liée aux LCOs nous ont permis de formuler un modèle qui a été utilisé pour trouver d'une façon analytique la courbe de réponse de phase (PRC) qui caractérise un LCO.<p><p>Le modèle a ensuite été validé en comparant les résultats expérimentaux et théoriques. Le modèle reproduit même, le phénomène de bifurcation qui apparaît lorsque trois LCOs sont couplés et disposés en ligne :deux états stables différents apparaissent selon les conditions initiales. L'accord trouvé entre théorie et expérience nous permet d'utiliser le modèle pour étudier d'autres situations qui ne sont pas facilement abordables du point de vue expérimental.<p><p>Nous avons étudié analytiquement deux LCOs identiques couplés. Même pour ce cas idéal, nous étions obligés de faire des simplifications pour pouvoir trouver des solutions exactes. On a trouvé pour ce système deux états possibles qui dépendent des conditions initiales, la synchronisation (stable) et l'anti-synchronisation (instable). Nous avons également montré que le temps de synchronisation augmente avec la distance entre LCOs. La construction des langues d'Arnold (régions de synchronisation) nous a permis de distinguer des régions de synchronisation pure d'ordre n:m et des régions de superposition synchronisation--modulation.<p><p>Nous avons travaillé numériquement avec des systèmes de LCOs affectés de bruits uniforme et Gaussien. Le comportement synchrone de ce système a été caractérisé en utilisant des paramètres statistiques simples tels que la moyenne de la différence de phase linéaire et la variance de la différence de phase cyclique. Nous avons démontré que le bruit, bien qu'il puisse perturber la synchronisation, peut aussi la favoriser entre deux LCOs qui ne se synchroniseraient pas en conditions normales, surtout quand le bruit est Gaussien et que les variances du bruit ne sont pas égales.<p><p>Nous avons étudié en termes statistiques la synchronisation de LCOs couplés localement et arrangés en ligne, en anneau et en réseau. Nous avons montré que la synchronisation totale se produit plus facilement pour des LCOs disposés en anneau. Concernant le temps de synchronisation, il est imprédictible. Les résultats analytiques et numériques suggèrent que la synchronisation totale est le phénomène le plus probable quand le nombre d'oscillateurs n'est pas très grand.<p><p>Finalement, nous avons étudié des LCOs statiques et mobiles couplés globalement. Dans les deux cas, nous avons trouvé que la synchronisation est moins probable quand le nombre d'oscillateurs augmente. Pour la condition statique, en considérant un couplage du type champ moyen, nous avons observé que le temps de synchronisation diminue avec le nombre de LCOs. Cependant, pour la situation plus réaliste dans laquelle l'interaction entre LCOs dépend de la distance les séparant, le temps de synchronisation devient à nouveau imprédictible. Enfin, nous avons étudié l'influence de la mobilité sur la synchronisation, problème qui est important en biologie et en robotique.<p><p>Notre système, de par ses caractéristiques et sa base expérimentale, est beaucoup plus proche de la réalité que ceux considérés d'habitude dans la littérature. Les résultats obtenus peuvent s'appliquer à des systèmes biologiques (lucioles, cellules cardiaques, neurones, …), mais également à la robotique, où la communication à longue portée par la lumière et l'émergence de patterns de synchronisation pourraient être très utiles dans le but d'effectuer des tâches spécifiques. / Doctorat en sciences, Spécialisation physique / info:eu-repo/semantics/nonPublished

Through continued innovation and growth, traveling wave tube amplifiers (TWTAs) remains the microwave power amplifiers of choice in a wide range of high power microwave and millimeter-wave applications specifically for aerospace applications with the volume, weight, bandwidth and power constraints. These advances can be credited to device innovation, improved modeling and design and development of advanced materials and construction techniques. This thesis aims at advancing the present technology of TWTs with coupled resonator slow-wave structures (SWSs) by a combination of device innovation, development of enhanced analytical and field analysis codes and understanding gained through improved modeling, simulation and experimentation. In a TWT, the SWS that slows the RF wave velocity down to near the electron beam velocity for interaction with the electron beam primarily determines the microwave performances of the tube. As compared to helix SWS, the coupled resonator SWS is capable of handling high peak and average powers with higher efficiency and TWTs based on these SWS are well suited for air-borne or space-borne radar systems and the major focus of this thesis is on the analysis and design of coupled resonator SWSs. As a part of this thesis, improved analytical codes based on quasi-TEM analysis and equivalent circuit analysis have been developed. The technical formulation is explained and the improvements made for enhanced accuracy and for incorporation of different types of coupled resonator SWSs detailed. Using these models new variants of coupled resonator SWSs have been investigated. The SWSs proposed are the ladder-core inverted slot mode SWS and the inductively loaded inter digital SWS (ILID-SWS). The possibility of achieving both coalesced mode design that gives wide bandwidth and multi beam design that improves the peak power and gain using rectangular ILID-SWS is presented. The properties of these proposed SWSs have been compared with the existing SWSs and found to give superior performance. Also an improved modeling and simulation technique using 3-D electromagnetic codes has been proposed and the conventional cold test measurement procedure has been modified for more accurate results. Numerous illustrative examples are presented throughout the thesis highlighting the analytical model and simulation code validation with experimental results. The experimentations have been carried out on the real SWS model that have been fabricated and assembled. Further, the contribution of the thesis is towards the development of a field analysis model for analysis of a corrugated waveguide SWS, based on the coupled integral equation technique (CIET), which is a combination of mode matching technique (MMT) and method of moments. The technical formulation and computational methodology employed in the model are explained and some of the most important aspects of implementation like the handling of singularities and choice of parameters controlling the accuracy is discussed. The accuracy and speed of the code is demonstrated by comparing CIET with MMT and 3-D electro magnetic simulators based on finite difference time domain (FDTD) method and finite element method (FEM). The CIET code developed is quite faster than the existing numerical methods and helps in solving the convergence problem associated with the MMT.

In this thesis the application of novel tensor decomposition and tensor representation techniques in highly accurate post Hartree-Fock methods is evaluated. These representation techniques can help to overcome the steep scaling behaviour of high level ab-initio calculations with increasing system size and therefore break the "curse of dimensionality". After a comparison of various tensor formats the application of the "canonical polyadic" format (CP) is described in detail. There, especially the casting of a normal, index based tensor into the CP format (tensor decomposition) and a method for a low rank approximation (rank reduction) of the two-electron integrals in the AO basis are investigated. The decisive quantity for the applicability of the CP format is the scaling of the rank with increasing system and basis set size. The memory requirements and the computational effort for tensor manipulations in the CP format are only linear in the number of dimensions but still depend on the expansion length (rank) of the approximation. Furthermore, the AO-MO transformation and a MP2 algorithm with decomposed tensors in the CP format is evaluated and the scaling with increasing system and basis set size is investigated. Finally, a Coupled-Cluster algorithm based only on low-rank CP representation of the MO integrals is developed. There, especially the successive tensor contraction during the iterative solution of the amplitude equations and the error propagation upon multiple application of the reduction procedure are discussed. In conclusion the overall complexity of a Coupled-Cluster procedure with tensors in CP format is evaluated and some possibilities for improvements of the rank reduction procedure tailored to the needs in electronic structure calculations are shown. / Die vorliegende Arbeit beschäftigt sich mit der Anwendung neuartiger Tensorzerlegungs- und Tensorrepesentationstechniken in hochgenauen post Hartree-Fock Methoden um das hohe Skalierungsverhalten dieser Verfahren mit steigender Systemgröße zu verringern und somit den "Fluch der Dimensionen" zu brechen. Nach einer vergleichenden Betrachtung verschiedener Representationsformate wird auf die Anwendung des "canonical polyadic" Formates (CP) detailliert eingegangen. Dabei stehen zunächst die Umwandlung eines normalen, indexbasierten Tensors in das CP Format (Tensorzerlegung) und eine Methode der Niedrigrang Approximation (Rangreduktion) für Zweielektronenintegrale in der AO Basis im Vordergrund. Die entscheidende Größe für die Anwendbarkeit ist dabei das Skalierungsverhalten das Ranges mit steigender System- und Basissatzgröße, da der Speicheraufwand und die Berechnungskosten für Tensormanipulationen im CP Format zwar nur noch linear von der Anzahl der Dimensionen des Tensors abhängen, allerdings auch mit der Expansionslänge (Rang) skalieren. Im Anschluss wird die AO-MO Transformation und der MP2 Algorithmus mit zerlegten Tensoren im CP Format diskutiert und erneut das Skalierungsverhalten mit steigender System- und Basissatzgröße untersucht. Abschließend wird ein Coupled-Cluster Algorithmus vorgestellt, welcher ausschließlich mit Tensoren in einer Niedrigrang CP Darstellung arbeitet. Dabei wird vor allem auf die sukzessive Tensorkontraktion während der iterativen Bestimmung der Amplituden eingegangen und die Fehlerfortpanzung durch Anwendung des Rangreduktions-Algorithmus analysiert. Abschließend wird die Komplexität des gesamten Verfahrens bewertet und Verbesserungsmöglichkeiten der Reduktionsprozedur aufgezeigt.

Thesis (PhD)--Stellenbosch University, 2013. / ENGLISH ABSTRACT: In this work a robust reversed phase ion-pairing high performance liquid chromatographic (RP-HPLC) method has been developed for the separation, characterization and quantification of all possible [PtCl6-nBrn]2- (n = 0 – 6) and [PtCl4-nBrn]2- (n = 0 – 4) complex anions using UV-Vis detection. High resolution 195Pt NMR of more concentrated PtII/IV solutions served to validate the relevant species assignments, particularly those of the stereoisomer species, cis- and trans- [PtCl4Br2]2-, [PtCl2Br4]2- and mer- and fac-[PtCl3Br3]2-. Quantification of the PtII/IV species was achieved by means of IP-RP-HPLC coupled to either ICP-MS or ICP-OES, and together with the UV-Vis absorption spectra obtained by photodiode array (PDA) recording of all eluted species, allowed for the determination of the photometric characteristics (λmax and ε) of all the PtII/IV species. This data enables practical speciation studies of such PtII/IV complex anions using standard analytical equipment. The hyphenation of ion-pairing RP-HPLC to ICP-OES allows for the successful determination of the Pt to halide mole ratios of individually separated species in order to characterize these species in a novel manner. The Pt to chloride and/or Pt to bromide mole ratio of the [PtCl4]2- and the series of [PtCl6-nBrn]2- (n = 0 – 6) complexes were determined using HPLC-ICP-OES based on the 177.708 nm Pt, 134.724 nm Cl and 148.845 nm Br emission lines and served as a technique for the unambiguous chemical speciation of such complexes. An increase in sensitivity of the developed method was achieved by the use of an ion-pairing reversed phase ultra high performance liquid chromatography electrospray ionization quadrupole time-of-flight mass spectrometry (UHPLC-ESI-Q-TOF-MS) method. This method proved capable of separating and characterizing the homoleptic and heteroleptic [PtIVCl6-nBrn]2- (n = 0 – 6) and mono-aquated [PtIVCl5-nBrn(H2O)]- (n = 0 – 5) complex anions in well defined acidic aqueous solutions. Ion-pairing ultra high performance liquid chromatography separation based on the volatile ion-pairing reagent, tributylamine, provided adequate chromatographic resolution as well as sufficiently low background noise for high resolution ESI-Q-TOF-MS detection. The wealth of structural information contained in the mass spectra obtained for each PtIV species simplified the identification of individual species. Moreover, the general fragmentation trends encompassing a constant incremental change of 44 Da (79/81Br - 35/37Cl) resulting from the successive substitution of Cl- by Br-, in combination with the observed elution order, facilitated the relevant species assignments. The developed method enabled the relative rapid (<13 min) characterization of all 22 [PtCl6-nBrn]2- (n = 0 – 6) and mono-aquated [PtCl5-nBrn(H2O)]- (n = 0 – 5) species. Quantification of each individual [PtCl6-nBrn]2- (n = 0 – 6) species by means of ion-paring HPLC-UV-Vis allowed for the determination of all 17 stability constants for the PtIV chloridobromido halide exchange reaction network. Determination of the associated Gibbs free energies for each ligand exchange reaction step, o rxnK ΔG n (n = 1 - 17), together with energy conservation relationships, served to validate the accuracy of the experimentally calculated stability constants. The experimentally determined overall formation constant, or ΔGo rxn, and those calculated using the standard reaction half cell reduction potentials of [PtCl6]2- and [PtBr6]2- were in good agreement, further confirming the experimentally obtained thermodynamic parameters. The thermodynamic driving force for the PtIV chloride-bromido exchange reactions is attributed to the hydration of the halide ligands, which drives the reaction towards the bromido PtIV species in aqueous solutions, even though the chlorido PtIV complexes are energetically favoured in this reaction network. Evaluation of other metal cation halido exchange reactions shows that all metal halido complexes exhibit the F- >> Cl- > Br- > I- order of thermodynamic stability and is only inverted due to the solvation of the relevant halide ligands. Furthermore, density functional theory (DFT) was used to predict the thermodynamic stabilities with respect to the isodesmic reactions involving chlorido-bromido PtIV stereoisomer pairs and chlorido-bromido PtIV ligand exchange reactions of the [PtCl6-nBrn]2- (n = 0 – 6) species and confirm the F- >> Cl- > Br- > I- order of thermodynamic stability as well as determining the ΔΔGo rxn within the range of 8 - 20 kJ.mol-1 to the experimentally determined ΔΔGo rxn. / AFRIKAANSE OPSOMMING: Tydens hierdie studie is „n robuuste “reverse-phase” ioonparing hoë-verrigting vloeistof chromatografie, RP-IP-HPLC, metode ontwikkel vir die skeiding, karakterisering en kwantifisering van alle moontlike [PtCl6-nBrn]2- (n = 0 – 6) en [PtCl4-nBrn]2- (n = 0 – 4) kompleks anione waar UV-Vis as detektor gebruik word. Die relavante spesies toedelings wat gemaak is, veral ten opsigte van die cis- en trans-[PtCl4Br2]2-, [PtCl2Br4]2- en mer- en fac-[PtCl3Br3]2- stereo-isomeerpare, is deur middel van hoë-resolusie 195Pt KMR van meer gekonsentreerde PtII/IV oplossings bevestig. Die PtII/IV spesies was gekwantifiseer deur die IP-RP-HPLC aan of „n ICPMS of „n ICP-OES te koppel. Daarenbowe was dit moontlik om die fotometriese eienskappe (λmax en ε) van elke individuele PtII/IV komplex anion te bepaal deur die UV-Vis absorpsie spektrum van elke elueerende spesies met PDA op te neem. Die nuwe metode wat tydens hierdie studie ontwikkel is het dit dus moontlik gemaak om sulke PtII/IV komplek sanione met standaard analitiese toerusting prakties te skei. Verder is gevind dat deur IP-RP-HPLC aan ICP-OES te koppel dit moontlik is om die Pt tot halied mol verhoudings van elke individueel geskeide spesies te bepaal en dus hierdie spesies op „n oorspronklike, nuwe manier te karakteriseer. Die Pt tot chloried en/of Pt tot bromied mol verhoudings van die [PtCl4]2- en die reeks van [PtCl6-nBrn]2- (n = 0 – 6) kompleks anione, soos bepaal deur gebruik te maak van HPLC-ICP-OES, is gebasseer op die 177.708 nm Pt, 134.724 nm Cl en 148.845 nm Br emissie lyne. Hierdie metode kan gebruik word vir die eenduidige chemiese skeiding van hierdie komplekse. Die sensitiwiteit van hierdie metode was egter verder verbeter deur gebruik te maak van ioonparing “reverse-phase” ultra hoë-verrigting vloeistof chromatografie gekoppel met elektrosprei ionisasie quadropool “time-of-flight” massa spektrometrie (UHPLC-ESI-Q-TOFMS). Deur dit te doen is dit nou selfs moontlik om die homoleptiese en heteroleptiese [PtIVCl6-nBrn]2- (n = 0 – 6) spesies, asook die “mono-aqauted” [PtIVCl5-nBrnH2O]- (n = 0 – 5) spesies in „n goed gedefinieërde aangesuurde waterige oplossings te skei en te karakteriseer. Die vlugtige ioon-paringsreagent, tributielamien, is vir die skeidingsproses op die IP-UHPLC gebruik om te verseker dat voldoende chromatografiese resolusie, so wel as lae genoeg agtergrondgeraas, verkry word vir hoë-resolusie ESI-Q-TOF-MS deteksie. Die rykdom informasie vervat in die massaspektrum van elke PtIV spesies het die indentifikasie van elke spesies vergemaklik. Daarenbowe het die fragmentasie tendens, aanduidend van „n konstante inkrementele verandering van 44 amu (71/81Br – 35/37Cl) weens die opeenvolgende substitusie van Cl- met Br-, tesame met die elusie volgorde, die spesies-toedelings gefasiliteer. Met hierdie nuut ontwikkelde metode is dit nou moontlik om al 22 [PtCl6-nBrn]2- (n = 0 – 6) en “mono-aquated” [PtCl5-nBrnH2O]- (n = 0 – 5) spesies in „n relatiewe kort tydperk (< 13 min) te karakteriseer. Deurdat elke [PtCl6-nBrn]2- (n = 0 – 6) spesies nou individueel met IP-HPLC-UV-Vis gekwantifiseer kan word, is dit moontlik om al 17 stabiliteitskonstantes vir die PtIV chloridobromido halied uitruilingsreaksienetwerk te bepaal. Die geassosieerde Gibbs vrye energie, ΔG°rxnKn (n = 0 – 17), wat vir elke stap in die uitruilingsreaksienetwerk bepaal is, tesame met die energiebewaring verhoudings, was gebruik om die akkuraatheid van die eksperimenteel bepaalde stabiliteitskonstantes te bekragtig. Verdermeer was die waarde van die algehele formasie konstante wat eksperimenteel bepaal is, ΔG°rxn, in goeie ooreenstemming met dit wat bereken is deur die standaard reaksie halfsel reduksie potensiale van [PtCl6]2- en [PtBr6]2-. Dus is die eksperimenteel verkrygde termodinamiese parameters bevestig. Die termodinamiese dryfkrag vir die PtIV chloried-bromied uitruilingsreaksies is toegereken aan die hidrasie van die halied ligande, wat in waterige oplossings die reaksie na die bromied PtIV spesies dryf, al is die chloried PtIV spesies energeties bevoordeel in hierdie reaksienetwerk. Evaluering van ander metaalkatioon- halied-uitruilreaksies wys dat alle metaal-halied komplekse die F- >> Cl- > Br- > I- orde van termodinamiese stabiliteit volg en dat hierdie volgorde slegs omgekeer sal word weens solvasie van hierdie halied ligande. Darenbowe digtheids funksionele teorie (DFT) gebruik om die termodinamiese stabiliteit met betrekking tot isodesmiese reaksies wat chloried-bromied PtIV stereoisomeer pare behels te voorspel, sowel as van chloried-bromied PtIV liganduitruilingsreaksies van die [PtCl6-nBrn]2- (n = 0 – 6) spesies, en bevestig die F- >> Cl- > Br- > I- volgorde van termodinamiese stabiliteit. Verder was dit ook moontlik om met DFT die ΔΔG°rxn tot so naby as 8 – 20 kJ.mol-1 te bereken.

In this thesis, an analysis technique for the slot coupled patch antennas using MoM in conjunction with the closed form Green&rsquo / s functions is presented. Slot coupled patch antennas are fed by a microstrip open stub which is coupled to the patch through an electrically small slot. Current distributions over the microstrip line, slot line and the patch are represented by rooftop basis functions. First, a relatively simple structure, microstrip coupled slot line is investigated using the proposed technique. Then the method is extended to the slot coupled patch antenna geometry. By using the method, current distributions on the feedline and the patch are calculated for a generic slot coupled patch antenna. Then by using the distributions, return scattering parameters of the antenna is approximated with complex exponentials using Prony&rsquo / s method. A parametric study is carried out to observe the effect of each antenna component on the antenna performance. Current distributions and return loss calculations are repeated for modified antennas to observe and demonstrate the performance differences. All simulations are verified using HFSS&reg / software and the results available in the literature.

This thesis includes the design, production and measurement of a wideband dualpolarized X-band aperture-coupled microstrip patch antenna. The wideband and dual-polarized operation is achieved through the use of H-shaped coupling slots. Therefore, the equivalent circuit modeling of a microstrip line fed H-shaped slot is also studied in this thesis. A step-by-step procedure is followed during the design process of the dual-polarized aperture-coupled microstrip antenna. First, an aperture-coupled microstrip antenna with a single rectangular slot, that exhibits a wideband characteristic for single polarization, is designed. Then, the design procedure is repeated for an antenna with H-shaped slot in order to satisfy the same specifications with a shorter slot. Finally, dual-polarized aperture-coupled microstrip antenna is designed. At this configuration, two H-shaped slots are used and they are placed orthogonal to each other. During the design process, the effects of antenna parameters on the input impedance characteristics of the antenna are investigated. These parametric analyses are done in CST Microwave Studio&reg / . The v designed dual-polarized wideband aperture-coupled microstrip antenna is manufactured. Simulation results and measurement results are compared. During the equivalent circuit modeling of an H-shaped slot fed by a microstrip line, an approach based on the reciprocity theorem is utilized. The method was originally proposed for rectangular shaped slots, in this thesis it is generalized for arbitrarily shaped slots. Software codes are developed in MATLAB to calculate the equivalent impedance of the slot.

The goal of the current study was to develop a computational framework for modelling the coupled fluid-structure interaction problem of squeeze films often encountered in MEMS devices. Vibratory MEMS devices such as gyroscopes, RF switches, and 2D resonators often have a thin plate like structure vibrating transversely to a Fixed substrate, and are generally not perfectly vacuum packed. This results in a thin air film being trapped between the vibrating plate and the fixed substrate which behaves like a squeeze film offering both stiffness and damping to the vibrating plate. For accurate modelling of the squeeze film effect, one must account for the coupled fluid-structure interaction. The majority of prior works attempting to address the coupled problem either approximate the mode shape of the vibrating plate or resort to cumbersome iterative solution strategies to address the problem in an indirect way. In the current work, we discuss the development of a fully coupled finite element based numerical scheme to solve the 2D Reynolds equation coupled with the 3D plate elasticity equation in a single step. The squeeze film solver so developed has been implemented into a commercial FEA package NISA as part of its Micro-Systems module. Further, extending on a prior analytical work, the effect of variable ow boundaries for an all sides clamped plate on squeeze film parameters has been thoroughly investigated. The developed FEM based numerical scheme has been used to validate the results of the prior analytical study. The developed numerical scheme models the 2D Reynolds equation thus limiting the model to account for the effects of the fluid volume strictly confined between the structure and the substrate. To study the effect of surrounding fluid volume ANSYS FLOTRAN simulations have been performed by numerically solving the full 3D Navier Stokes equation in the extended fluid domain for the different flow boundary scenarios. Cut-off frequencies are established beyond which one can consider a 2D fluid domain without considerable loss of accuracy. First, a displacement based finite element formulation is presented for the 2D Reynolds equation coupled with the 3D elasticity equation. Both lower order 8 node and higher order 27 node 3D elements are developed. Only a single type of 3D element is used for modelling along with a 2D fluid layer represented by the \wet" face of the 3D structural domain. The results from our numerical model are compared with experimental data from literature for a MEMS cantilever. The results from the 27 node displacement based elements show good agreement with published experimental data. The results from the lower order 8 node displacement based elements however show huge errors even for relatively fine meshes due to locking issues in modelling high aspect ratio structures. This limits the implementation of the displacement based solver in commercial FE packages where the available mesh generators are generally restricted to lower order 3D elements. In order to overcome the limitations faced by lower order elements (primarily locking issues) in modelling high aspect ratio MEMS geometries, a coupled hybrid formulation is developed next. A thorough performance study is presented considering both the hybrid and displacement based elements for lower order 8 node and higher order 27 node ele- ments. The optimal element choice for modelling squeeze film geometries is determined based on the comparative studies. The effect of element aspect ratio for hybrid and displacement based elements are studied and the superiority of hybrid formulation over displacement based formulations is established for lower order 8 node elements. The coupled hybrid nite element formulation developed for lower order elements is implemented in the commercial FEA package NISA. The implementation scheme to integrate the developed coupled hybrid 8 node squeeze film solver into the commercial FEA package is discussed. The pre-integration analysis and subsequent requirement gaps are first investigated. Based on the gap analysis, certain GUI modifications are undertaken and parser programs are developed to re-format data according to NISA input requirements. Certain special features are included in the package to aid in post processing data analysis by MEMS designers such as \frequency sweep" and \node of interest" selection. As a case study for validation, we also present the modelling of a MEMS cantilever and show that the simulation results from our software are in good agreement with experimental data reported in the literature. Finally as a case study, an extension of a prior analytical work, which studies the effect of varying flow boundaries on squeeze film parameters, is discussed. Explanations are provided for the findings reported in the prior analytical work. The concept of using variation in flow boundaries as a frequency tuning tool is introduced. The analytical results are validated with the coupled numerical scheme discussed before, by considering imposed mode shape for an all sides clamped plate as prescribed displacement to the fluid domain. The simulated results are used to study the intricacies in squeeze film damping and stiffness variations with respect to spatial changes in the fluid flow boundary conditions. In particular, it has been shown that the boundary venting conditions can be used effectively to tune the dynamic response of a micromechanical structure over a fairly large range of frequencies and somewhat smaller range of squeeze film damping. Next, the effect of the surrounding fluid volume for various venting conditions is studied. ANSYS FLOTRAN is used to solve for the full 3D Navier Stokes equation over the extended fluid domain. Results from the extended domain study are used to determine cut-off frequencies beyond which one need not resort to an extended mesh study, and yet be within 5% accuracy of the full extended mesh model.

Orientador: Pedro Antonio Muniz Vazquez / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-14T17:56:25Z (GMT). No. of bitstreams: 1 Vidal_LucianoNassif_D.pdf: 1273955 bytes, checksum: 79e28497883fdc3e8ebe5907183a15d9 (MD5) Previous issue date: 2009 / Resumo: O presente trabalho aborda o desenvolvimento de metodologias para o cálculo das intensidades absolutas do espalhamento Raman vibracional produzido por moléculas em fase gasosa. Com o objetivo de reduzir a demanda por recursos computacionais nestes cálculos, foram desenvolvidas duas novas famílias de funções de base compactas pela aplicação do método de polarização elétrica de Sadlej às bases para uso com potenciais efetivos de caroço SBKJC e de Stuttgart-Colônia. Utilizando estas novas funções de base, as intensidades Raman podem ser obtidas com a mesma qualidade das bases Sadlej-pVTZ, que são referência no cálculo destas propriedades, porém com um custo computacional sensivelmente menor. Além disso, como estes pseudopotenciais foram modelados para descrever os efeitos relativísticos sobre os elétrons internos, as polarizabilidades e intensidades Raman obtidas no nível Hartree-Fock com estas novas bases concordam, dentro de um erro médio de 6%, com seus respectivos valores relativísticos Dirac-Hartree-Fock/Sadlei-pVTZ com hamiltoniano de Dirac-Coulomb. Também foi desenvolvida uma metodologia para o estudo das intensidades das transições Raman fundamentais, de combinação e sobretom, que inclui as correções para a anarmonicidade cúbica do potencial, introduzidas através de uma transformação de contato. Os resultados obtidos para a molécula de acetileno e seus isotopômeros deuterados mostram que a anarmonicidade mecânica exerce grande influência sobre as intensidades Raman, particularmente das transições de segunda ordem. Excetuando as transições de combinação, em geral, as correções de anarmoniciadade melhoram a concordância dos valores teóricos com os experimentais. Uma terceira parte deste trabalho trata do efeito Raman em condições ressonantes, onde uma expressão para estas intensidades foi derivada, implementada no programa PLACZEK e aplicada no cálculo do espectro Raman da molécula de trans-butadieno nas vizinhanças de sua transição eletrônica 1Bu. Este estudo mostrou que as aproximações utilizadas com maior frequência para simplificar o cálculo desta propriedade afetam significativamente as seções de choque desta molécula, sugerindo que estas aproximações devem ser evitadas em estudos desta natureza. / Abstract: In this work new methodologies for the calculation of absolute vibrational Raman intensities of gaseous systems are presented. In order to reduce the computational requirements in these calculations two families of compact basis functions were generated from the effective core potential valence basis sets SBKJC and Stuttgart-Cologne through the Sadlej's electric polarization procedure. The Raman intensities evaluated with the new bases are close to those obtained with the well successful Sadlej-pVTZ basis but the computational requirements are significatively reduced. Furthermore, since the effective core potentials SBKJC and Stuttgart-Cologne were developed to account for the relativistic effects on the inner electrons, the polarizabilities and Raman intensities evaluated at the Hartree-Fock level with the new bases agree with the relativistic Dirac-Hartree-Fock values, obtained using the Dirac-Coulomb Hamiltonian and the Sadlej-pVTZ set, within the mean error of 6%. In the second part of this work a methodology was developed for the study of fundamental, combination and overtone Raman transitions including a treatment based on the contact transform formalism for the mechanical anharmonicity from the cubic potential energy terms. The results obtained for acetylene and its deutered isotopomers show that anharmonicity effects on the Raman intensities can be very strong, particularly in the second order transitions. With the exception of the combination transitions, in general the corrections for mechanical anharmonicity improve the agreement between ab initio and experimental values. The resonance Raman scattering is the subject of the third part of this work where an expression for the resonance cross section was derived, implemented in the PLACZEK program and applied to the calculation of the resonance Raman spectrum of the trans-butadiene molecule in the region of its. / Doutorado / Físico-Química / Doutor em Ciências

Les déchets solides générés par notre société sont nombreux. Les cendres volantes sont des déchets solides produits lors de la combustion de déchets domestiques ou industriels dans des incinérateurs. Les cendres volantes sont également produites par la combustion du charbon dans les centrales à charbon. Les cendres volantes sont des résultats de ces combustions et représentent importante quantité de déchets produits chaque année par notre société. Les possibilités de recyclage de ces déchets sont nombreuses : dans la construction, l'industrie routière. Elles sont également stockées pour une utilisation ultérieure. Les origines différentes des charbons et déchets incinérés conduisent à une minéralogie et une composition élémentaire complexe. En tant que sous-produit le devenir des cendres volantes est important à déterminer, aussi la détermination de la composition élémentaire de ces cendres volantes est-elle indispensable.Les méthodes classiques de préparation des échantillons solides sont la minéralisation acide ou la fusion alcaline. Ces procédures prennent du temps et supposent l’utilisation de réactif, de plus la digestion complète n'est pas toujours assurée. Le risque de contamination par les réactifs employés est important au cours de ces méthodes classiques de préparation. Au cours de la dernière décennie, le développement d’analyse directe d'échantillons solides en utilisant des méthodes d'ablation laser a été important en raison de la nécessité de réduire le temps d'analyse et de réduire aussi la consommation de réactifs. Dans ce travail, deux méthodes basées sur l'ablation par laser seront étudiées pour l'analyse des cendres: Laser Induced Breakdown Spectroscopy (LIBS) et Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS). La spectrométrie LIBS sera étudiée pour la détermination quantitative des éléments majeurs dans les échantillons de cendres alors que le couplage ablation laser ICP / MS sera employé pour détermination des éléments traces. L'optimisation de la sensibilité et les stratégies d'étalonnage sont les principaux problèmes traités dans ce travail. La préparation des échantillons et l’optimisation ont été effectuées pour déterminer les éléments tels que Al, As, Ba, Ca, Cr, Cu, Fe, Mg, Mn, Pb, Sr, V et Zn par les deux méthodes.Les performances analytiques telles que les limites de détection, justesse ont été obtenus à la suite d'optimisations appropriées des liants et de la sélection de l’étalon interne approprié. En conclusion, l’analyse directe de solides en utilisant les techniques basées sur l’ablation laser développées dans ce travail conduisent à une justesse acceptable pour la détermination des éléments majeurs et traces dans les cendres volantes / Solid waste generated by our society are numerous, fly ashes are produced during the combustion of domestic or industrial waste in incinerators. Fly ashes are also produced through coal combustion in coal fired power plants. Fly ashes are results of these combustions and represent important quantity of waste produced every year by our society. They have variable use – in construction, road industry, or they can be stocked for further use. As they are result of different origin, they have complex mineral and elemental composition. As a by-product or as a recycled product fly ashes fate is important to determine. In this view the determination of the elemental composition of fly ashes is the aim of this work.Conventional methods of sample preparation are acid digestion or alkali fusion. These procedures are time and reagent consuming and complete digestion is not assured. The potential contamination of the reagents employed is important during these classical sample preparation methods. During the past decade, development of direct solid sampling using laser ablation methods was important due to the need of reducing analysis time and also reducing reagent consumption. In this work, two methods based on laser ablation will be studied for fly ash analysis: Laser Induced Breakdown Spectroscopy (LIBS) and Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS). LIBS will be studied for quantitative determination of major elements in fly ash samples while Laser ablation / ICP MS will be employed for trace element determination.The sensitivity optimization and different calibration strategies are key problems of laser sampling methods. Sample preparation and condition optimisation were performed to determine major, minor and trace elements such as Al, As, Ba, Ca, Cr, Cu, Fe, Mg, Mn, Pb, Sr, V and Zn by both methods – LIBS for major elements and LA-ICP-MS for minor and trace elements.Analytical properties such as detection limits, accuracy and analytical working curves were obtained following suitable optimisation of binders and internal standards. Compromise binder and analytical conditions were selected to determine the elements in fly ash samples.In conclusion, direct solid sampling using laser ablation followed by LIBS or for solid introduction into ICP was found to determine major, minor and trace elements in fly ashes, improving pellets mechanical stability, high samples sensitivity and acceptable accuracy and detection limits.

The field of coupled resonant systems is a rich research area with enumerable real-world applications, including the fields of neural computing and pattern recognition, energy harvesting, and even modeling the behavior of certain types of biological systems. This work is primarily focused on the study of the behaviors of two subsets of this field: large networks of globally coupled resonators (which, in this work, refers to passive, damped resonant elements which require external stimulus) and smaller networks of oscillators (referring to active devices capable of self-sustained motion), which are coupled through a network of light-sensitive resistive elements. In the case of the former, we begin by developing an analytical and experimental framework to examine the behaviors of this system under various conditions, such as different coupling modalities and element-level parametric mistunings. Once a proper understanding of the dynamics of these systems has been established, we go on to develop the system into a single-input, single-output, multi-analyte volatile organic compound sensor. For the study of oscillator networks, we begin by building a device which utilizes a network of Colpitts oscillators, coupled through a series of color-filtered CdSe photocells. We then establish that through the analysis of particular emergent behaviors (most notably, frequency locking within the network), this type of system may show promise as a threshold color sensor. By exploiting these behaviors, this type of system may find applications in neuromorphic computing (particularly in optical pattern recognition).