In this dissertation, we have proposed two new algorithms for statistical inference for models with intractable normalizing constants: the Monte Carlo Metropolis-Hastings algorithm and the Bayesian Stochastic Approximation Monte Carlo algorithm. The MCMH algorithm is a Monte Carlo version of the Metropolis-Hastings algorithm. At each iteration, it replaces the unknown normalizing constant ratio by a Monte Carlo estimate. Although the algorithm violates the detailed balance condition, it still converges, as shown in the paper, to the desired target distribution under mild conditions. The BSAMC algorithm works by simulating from a sequence of approximated distributions using the SAMC algorithm. A strong law of large numbers has been established for BSAMC estimators under mild conditions. One significant advantage of our algorithms over the auxiliary variable MCMC methods is that they avoid the requirement for perfect samples, and thus it can be applied to many models for which perfect sampling is not available or very expensive. In addition, although the normalizing constant approximation is also involved in BSAMC, BSAMC can perform very robustly to initial guesses of parameters due to the powerful ability of SAMC in sample space exploration. BSAMC has also provided a general framework for approximated Bayesian inference for the models for which the likelihood function is intractable: sampling from a sequence of approximated distributions with their average converging to the target distribution. With these two illustrated algorithms, we have demonstrated how the SAMCMC method can be applied to estimate the parameters of ERGMs, which is one of the typical examples of statistical models with intractable normalizing constants. We showed that the resulting estimate is consistent, asymptotically normal and asymptotically efficient. Compared to the MCMLE and SSA methods, a significant advantage of SAMCMC is that it overcomes the model degeneracy problem. The strength of SAMCMC comes from its varying truncation mechanism, which enables SAMCMC to avoid the model degeneracy problem through re-initialization. MCMLE and SSA do not possess the re-initialization mechanism, and tend to converge to a solution near the starting point, so they often fail for the models which suffer from the model degeneracy problem.

<p>The fascinating optical properties of metallic nanostructures, dominated by collective oscillations of free electrons known as plasmons, open new opportunities for the development of devices fabrication based on noble metal nanoparticle composite materials. This thesis demonstrates a low-cost and versatile technique to produce stimuli-responsive ultrafast plasmonic nanostructures with reversible tunable optical properties. Albeit challenging, further control using thermal external stimuli to tune the local environment of gold nanoparticles embedded in VO2 host matrix would be ideal for the design of responsive functional nanocomposites. We prepared Au-VO2 nanocomposite thin films by the inverted cylindrical reactive magnetron sputtering (ICMS) known as hollow cathode magnetron sputtering for the first time and report the reversible tuning of surface plasmon resonance of Au nanoparticles by only adjusting the external temperature stimuli. The structural, morphological, interfacial analysis and optical properties of the optimized nanostructures have been studied. ICMS has been attracting much attention for its enclosed geometry and its ability to deposit on large area, uniform coating of smart nanocomposites at high deposition rate. Before achieving the aforementioned goals, a systematic study and optimization process of VO2 host matrix has been done by studying the influence of deposition parameters on the structural, morphological and optical switching properties of VO2 thin films. A reversible thermal tunability of the optical/dielectric constants of VO2 thin films by spectroscopic ellipsometry has been intensively also studied in order to bring more insights about the shift of the plasmon of gold nanoparticles imbedded in VO2 host matrix.</p>

Many contemporary experimental QCD results achieve greater accuracy in measurement than equivalent theoretical predictions calculated at leading order. Therefore it is necessary to consider next to leading order (NLO) predictions for many processes in order to compare experiment with theory. Accurate theoretical predictions are also important in order to reduce the uncertainty in QCD parameters such as the coupling constant a, and to test whether QCD is in fact the correct theory to describe the strong interaction. With NLO results it is also possible to separate different clustering algorithms and test non-perturbative effects. This thesis concentrates on the techniques necessary for the calculation of NLO observables from the processes e(^+)e(^-) → 4 jets and pp → γ + X. We formulate a new version of the hybrid subtraction scheme based on the colour antenna structure of the final state to evaluate the necessary phase space integrals for the 4 jet process. The scheme is universal and can be applied to any QCD processes. The general purpose Monte Carlo EERAD2 which incorporates this new technique is compared with both experimental data gathered by the DELPHI collaboration and other groups which have reported similar calculations. A Monte Carlo written for the process pp → γ + X requires a knowledge of the non- perturbative photon fragmentation function, D(_γ), and the second half of this thesis concentrates on a calculation of this process using the ALEPH measurement of D(_γ) based on a democratic algorithm. The Monte Carlo DPRAD incorporates these techniques and results from it are compared with data from the Tevatron.

In this Thesis, we study some of the classical properties of an extension of the Skyrme model defined by adding a sixth order derivative term to the Lagrangian. In chapter 1, we review the physical as well as the mathematical motivation behind the study of the Skyrme model and in chapter 2, we give a brief summary of various extended Skyrme models that have been proposed over the last few years. We then define a new sixth order Skyrme model by introducing a dimensionless parameter λ that denotes the mixing between the two higher order terms, the Skyrme term and the sixth order term. In chapter 3 we compute numerically the multi-skyrmion solutions of this extended model and show that they have the same symmetries with the usual skyrmion solutions. In addition, we analyse the dependence of the energy and radius of these classical solutions with respect to the coupling constant λ. We compare our results with experimental data and determine whether this modified model can provide us with better theoretical predictions than the original one. In chapter 4, we use the rational map ansatz, introduced by Houghton, Manton and Sutcliffe, to approximate minimum energy multi-skyrmion solutions with B ≤ 9 of the SU(2) model and with B ≤ 6 of the SU(3) model. We compare our results with the ones obtained numerically and show that the rational map ansatz works just as well for the generalised model as for the pure Skyrme model, at least for B ≤ 5. In chapter 5, we use a generalisation of the rational map ansatz, introduced by loannidou, Piette and Zakrzewski, to construct analytically some topologically non-trivial solutions of the extended model in SU(3). These solutions are spherically symmetric and some of them can be interpreted as bound states of skyrmions. Finally, we use the same ansatz to construct low energy configurations of the SU(N) sixth order Skyrme model.

The purpose of this study was to investigate the fundamental characteristics of a chelating surfactant in terms of solution behaviour, chelation of divalent metal ions, and interaction in mixtures with different foaming agents and divalent metal ion, as well as examining its prospects in some practical applications. Chelating surfactants are functional molecules, with both surface active and chelating properties, which are water soluble and therefore suitable for chelation in many aqueous environments. The dual functionality offers the possibility to recover the chelating surfactant as well as the metals. The DTPA (diethylenetriaminepentaacetic acid)-based chelating surfactant 4-C12-DTPA (2-dodecyldiethylenetriaminepentaacetic acid) was synthesized at Mid Sweden University. In the absence of metal ions, all eight donor atoms in the headgroup of 4-C12-DTPA are titrating and the headgroup charge can be tuned from +3 to -5 by altering the pH. The solution properties, studied by surface tension measurements and NMR diffusometry, were consequently found strongly pH dependent. pH measurements of chelating surfactant solutions as a function of concentration was used to extract information regarding the interaction between surfactants in the aggregation process. Small differences in the conditional stability constants (log K) between coordination complexes of DTPA and 4-C12-DTPA, determined by competition measurements utilizing electrospray ionization mass spectrometry (ESI-MS), indicated that the hydrocarbon tail only affected the chelating ability of the headgroup to a limited extent. This was further confirmed in hydrogen peroxide bleaching of thermomechanical pulp (TMP) treated with 4-C12-DTPA. Interaction parameters for mixed systems of 4-C12-DTPA and different foaming agents were calculated following the approach of Rubingh’s regular solution theory. The mixtures were also examined with addition of divalent metal ions in equimolar ratio to the chelating surfactant. Strong correlation was found between the interaction parameter and the phase transfer efficiency of Ni2+ ions during flotations. Furthermore, a significant difference in log K between different metal complexes with 4-C12-DTPA enabled selective recovery of the metal ion with the highest log K. The findings in this study contribute to the understanding of the fundamental characteristics of chelating surfactants, which can be further utilized in practical applications.

This thesis describes procedures and theory for a family of one-sided ultrasonic methods for determining third order elastic constants (TOEC) using sets of angle-beam wedges mounted on one side of a specimen. The methods are based on the well-known acoustoelastic effect, which is the change of wave speed with applied loads and is a consequence of the mechanical nonlinearity of a material. Increases in material nonlinearity have been correlated to the progression of damage, indicating that tracking changes in TOECs may provide a practical means of monitoring damage accumulation at the microstructural level prior to formation of macroscopic defects. Ultrasonic methods are one of the only ways to measure TOECs, and most prior techniques have utilized wave propagation paths parallel and perpendicular to the loading directions. A few additional ultrasonic techniques reported in the literature have employed oblique paths but with immersion coupling. These reported techniques are generally unsuitable for field implementation. The one-sided contact approach described here is applicable for in situ measurements of TOECs and thus lays the foundation for tracking of TOECs with damage. Theory is reviewed and further developed for calculating predicted velocity changes, and thus time shifts, as a function of uniaxial tensile loading for longitudinal, shear vertical, and shear horizontal waves in the context of angle-beam transducers mounted on the surface of the specimen. A comparison is made to published results where possible. The inverse problem of determining the three TOECs of an isotropic material from three measurements employing three different angle beam configurations is comprehensively analyzed. Four configurations providing well-posed solutions are identified and examined. A detailed sensitivity analysis is carried out to identify the best mounting configuration, wave mode combinations, refracted angles and geometry requirements for recovering the three TOECs. Two transducer mounting configurations are considered: (1) attached (glued-on) transducers potentially suitable for in situ monitoring, and (2) floating (oil-coupled) transducers potentially suitable for single measurements. Limited experimental results are presented for the attached case using two longitudinal measurements and one shear vertical measurement. The floating case experiments utilized three of the four well-posed solutions, and measurements were made on several aluminum alloys and low carbon steel. Key experimental issues are identified and discussed for both transducer mounting configurations.

Η δυναμική ανάλυση των ηλεκτρικών μηχανών αποτελεί ένα πολύ σημαντικό πεδίο της μελέτης των ηλεκτρομηχανικών συστημάτων. Στην παρούσα διπλωματική θα ασχοληθούμε με τη δυναμική ανάλυση της σύγχρονης μηχανής που συναντάμε στην μετατροπή μεγάλης ποσότητας μηχανικής ενέργειας σε ηλεκτρική. Στόχος της παρούσας διπλωματικής είναι η μελέτη της συμπεριφοράς της σύγχρονης μηχανής σε περίπτωση μεταβατικών φαινόμενων, καθώς, επίσης, ο προσδιορισμός των μεγεθών, των παραμέτρων και των σταθερών χρόνου της μηχανής, που καθορίζουν τη συμπεριφορά της, στην περίπτωση τέτοιων φαινομένων. Οι χαρακτηριστικές παράμετροι των μεταβατικών και υπομεταβατικών αντιδράσεων και των σταθερών χρόνου της σύγχρονης μηχανής που επιχειρήθηκαν να προσδιοριστούν, χρησιμοποιούνται εδώ και 75 χρόνια, ώστε να δίνουν μια πρώτη προσέγγιση του μεγέθους των ρευμάτων βραχυκυκλώματος καθώς και το ρυθμό με τον οποίο αυτά μειώνονται. Επιπροσθέτως, η γνώση των μεγεθών αυτών δίνει τη δυνατότητα υπολογισμού των μηχανικών καταπονήσεων των τυλιγμάτων του στάτη που είναι αποτέλεσμα των υπερβολικών ρευμάτων που διαρρέουν τη μηχανή κατά τη διάρκεια ηλεκτρικών διαταραχών που υφίστανται οι ακροδέκτες της. / The dynamic analysis of electrical machines constitutes a very important field of the study of electromechanical systems. In the present project we will deal with the dynamic analysis of synchronous machine that we meet in the transformation of mechanical energy into electrical. The goal of present thesis is the study of the behavior of synchronous machine in case of transient phenomena and the determination of the parameters and time constants that determine its operation in such phenomena. The characteristic parameter of transient and subtransient reactances and time constants of synchronous machines that we tried to determine, have been used about 75 years, and for many purposes. Initially, such reactances and time constants were calculated to give both machine designers, and users, of synchronous machines a first-hand knowledge of-short-circuit current magnitudes and their rate of change. Such magnitudes are important in establishing switchgear fault rating. This knowledge also enables mechanical stresses to be calculated between armature winding resulting from excessive currents that occur during electrical disturbances at or near the synchronous machines terminals. In addition, protective schemes could be devised so that relays could be correctly calibrated to trip armature or field circuit breakers, and thus remove faulted machines from the power systems.

Pastilhas de dióxido de urânio (UO2) são empregadas como combustível nos reatores nucleares de potência, onde as condições operacionais introduzem elevados gradientes térmicos nas pastilhas. Potências elevadas propiciam a fusão da parte central das pastilhas. O inchamento das pastilhas de dióxido de urânio (UO2), decorrente dos produtos de fissão, pode causar o trincamento do material, em função disso, o estudo do seu comportamento mecânico é importante. Esse trabalho avaliou a aplicação de método ultrassônico na obtenção de constantes elásticas. Em função das dificuldades no manuseio do material nuclear, optou-se por um estudo comparativo em pastilhas de alumina (Al2O3). Foram fabricados e usados dois conjuntos de 10 pastilhas de Al2O3 com densidades de 92% e 96%. Foi desenvolvida técnica ultrassônica por transmissão obtendo medidas do tempo de percurso de ondas ultrassônicas, longitudinais e transversais, usadas para a determinação das constantes elásticas do material. Equações relacionando a velocidade da onda ultrassônica ao módulo de elasticidade, módulo de cisalhamento e coeficiente de Poisson, permitiram obter essas constantes elásticas, que apresentaram excelente concordância com a literatura disponível para o Al2O3.

The interaction between the amino acid glutathione (GSH) and zinc (II) and cadmium (II) ions was investigated using data obtained by potentiometric and voltammetric measurements. Solutions with ionic strength 0.1 M KCl with different metal-ligand ratios were titrated with standard solution of KOH and the pH profiles obtained were used to propose models of chemical equilibrium between the species. The potentiometric data treatment was performed using the Hyperquad software, which enabled that the formation constants of the differents pecies could be refined. The program HySS,belonging to the Hyperquad computer package, was used to obtain the species distribution curves. The best fit models of equilibrium was reached suggesting the existence of species in which the metal ions were coordinated by one and two molecules of the ligand, and the highest values were found for log β complex type MH2L, MHL2 and ML2. For the voltammetric data, multivariate curve resolution with alternating least squares (MCR-ALS) was applied. Several voltammograms recorded at different metal-ligand ratios generated a series of overlapping peaks, from which it was possible to recover the pure voltammograms and their concentration profiles applying non-negativity, unimodality and "closure" as constraints. For both systems studied (GSH-Zn and GSH-Cd), voltammograms were resolved to three components, the free metal and two complexes. The potentiometric and voltammetric data treated with MCR-ALS were capable to complement one another, constituting a important tool in the investigation of chemical equilibria between metal ions and ligands. / A interação entre o aminoácido glutationa (GSH) e os íons zinco (II) e cádmio (II) foi investigada a partir de dados obtidos por medidas potenciométricas e voltamétricas. Soluções com força iônica 0,1 M de KCl de diferentes proporções metal-ligante foram tituladas com solução padrão de KOH e os perfis de pH assim obtidos foram usados para propor os modelos de equilíbrio químico entre as espécies. Para tratar os dados potenciométricos foi utilizado o programa Hyperquad, possibilitando que as constantes de formação das diferentes espécies pudessem ser refinadas. O programa HySS, pertencente ao pacote computacional do Hyperquad, foi utilizado para obtenção as curvas de distribuição das espécies. O melhor ajuste dos modelos de equilíbrio foi alcançado propondo a existência de espécies em que os íons metálicos foram coordenados por uma e duas moléculas do ligante, sendo que os maiores valores de log β foram encontrados para os complexos do tipo MH2L, MHL2 e ML2. Para os dados voltamétricos, foi aplicado o método de resolução multivariada de curvas com mínimos quadrados alternantes (MCR-ALS). Vários voltamogramas registrados a diferentes proporções metal-ligante geraram uma série de picos sobrepostos, a partir dos quais foi possível recuperar os voltamogramas puros e respectivos perfis de concentração aplicando não negatividade, unimodalidade e closure como restrições. Para ambos os sistemas estudados (GSH-Zn e GSH-Cd) os voltamogramas foram resolvidos para três componentes, o metal livre e dois complexos. A potenciometria e a voltametria submetida a MCR-ALS mostraram-se capazes de se complementarem, constituindo-se em grandes ferramentas na investigação de equilíbrios químicos entre íons metálicos e ligantes.

Pastilhas de dióxido de urânio (UO2) são empregadas como combustível nos reatores nucleares de potência, onde as condições operacionais introduzem elevados gradientes térmicos nas pastilhas. Potências elevadas propiciam a fusão da parte central das pastilhas. O inchamento das pastilhas de dióxido de urânio (UO2), decorrente dos produtos de fissão, pode causar o trincamento do material, em função disso, o estudo do seu comportamento mecânico é importante. Esse trabalho avaliou a aplicação de método ultrassônico na obtenção de constantes elásticas. Em função das dificuldades no manuseio do material nuclear, optou-se por um estudo comparativo em pastilhas de alumina (Al2O3). Foram fabricados e usados dois conjuntos de 10 pastilhas de Al2O3 com densidades de 92% e 96%. Foi desenvolvida técnica ultrassônica por transmissão obtendo medidas do tempo de percurso de ondas ultrassônicas, longitudinais e transversais, usadas para a determinação das constantes elásticas do material. Equações relacionando a velocidade da onda ultrassônica ao módulo de elasticidade, módulo de cisalhamento e coeficiente de Poisson, permitiram obter essas constantes elásticas, que apresentaram excelente concordância com a literatura disponível para o Al2O3.