Study of the second hyperpolarizability of poly(3-alkylthiophenes) using the third-harmonic scattering technique

During the past years, the considerable need in the domain of communications for more potent photonic devices has focused the research activities into the nonlinear optical (NLO) materials which can be used for modern optical switches. In this regard, a lot of research activities are focused on the organic materials and conjugated polymers which offer more advantages compared to the inorganic ones. On this matter, poly(3-alkylthiophene) (P3AT), an organic conjugated polymer, can be investigated as potential optical material with in particular the focus on the NLO properties such as the first- and second-hyperpolarizability, β and γ respectively. The activities carried out at the Laboratory of Polymer Synthesis of the KU Leuven, during the master's thesis work, focused on the study of conjugated polymers in order to evaluate their NLO properties for the future purpose of applications in optical systems. In particular, three series of polythiophenes functionalized with an alkyl side chain in the 3-position were synthesized: poly(3-hexylthiophene) (P3HT), poly[3-(2-ethylhexyl)thiophene] (P3EHT) and random copolymer of the two regio-isomers of P3HT. They were made in order to study the influence of molar mass, branching and regio-irregularity on the γ-value. The Kumada catalyst transfer condensative polymerization (KCTCP) and the Pd(RuPhos)-protocol were used for the polymerizations in order to have control over the molar mass of the growing chain and consequently to obtain well-defined and reproducible materials. The P3AT derivatives obtained were characterized by gel permeation chromatography (GPC), spectroscopic techniques (1H-NMR, UV-Vis) and the γ-value was investigated using the third-harmonic scattering (THS) technique. In particular, the THS technique is useful to investigate the optical behavior of the series of polymers in solution.

Calculation of the eigenfunctions of the two-group neutron diffusion equation and application to modal decomposition of BWR instabilities

In this thesis, numerical methods aiming at determining the eigenfunctions, their adjoint and the corresponding eigenvalues of the two-group neutron diffusion equations representing any heterogeneous system are investigated. First, the classical power iteration method is modified so that the calculation of modes higher than the fundamental mode is possible. Thereafter, the Explicitly-Restarted Arnoldi method, belonging to the class of Krylov subspace methods, is touched upon. Although the modified power iteration method is a computationally-expensive algorithm, its main advantage is its robustness, i.e. the method always converges to the desired eigenfunctions without any need from the user to set up any parameter in the algorithm. On the other hand, the Arnoldi method, which requires some parameters to be defined by the user, is a very efficient method for calculating eigenfunctions of large sparse system of equations with a minimum computational effort. These methods are thereafter used for off-line analysis of the stability of Boiling Water Reactors. Since several oscillation modes are usually excited (global and regional oscillations) when unstable conditions are encountered, the characterization of the stability of the reactor using for instance the Decay Ratio as a stability indicator might be difficult if the contribution from each of the modes are not separated from each other. Such a modal decomposition is applied to a stability test performed at the Swedish Ringhals-1 unit in September 2002, after the use of the Arnoldi method for pre-calculating the different eigenmodes of the neutron flux throughout the reactor. The modal decomposition clearly demonstrates the excitation of both the global and regional oscillations. Furthermore, such oscillations are found to be intermittent with a time-varying phase shift between the first and second azimuthal modes.

A new insight in stress recovery tecniques and hessian reconstruction methods

Stress recovery techniques have been an active research topic in the last few years since, in 1987, Zienkiewicz and Zhu proposed a procedure called Superconvergent Patch Recovery (SPR). This procedure is a last-squares fit of stresses at super-convergent points over patches of elements and it leads to enhanced stress fields that can be used for evaluating finite element discretization errors. In subsequent years, numerous improved forms of this procedure have been proposed attempting to add equilibrium constraints to improve its performances. Later, another superconvergent technique, called Recovery by Equilibrium in Patches (REP), has been proposed. In this case the idea is to impose equilibrium in a weak form over patches and solve the resultant equations by a last-square scheme. In recent years another procedure, based on minimization of complementary energy, called Recovery by Compatibility in Patches (RCP) has been proposed in. This procedure, in many ways, can be seen as the dual form of REP as it substantially imposes compatibility in a weak form among a set of self-equilibrated stress fields. In this thesis a new insight in RCP is presented and the procedure is improved aiming at obtaining convergent second order derivatives of the stress resultants. In order to achieve this result, two different strategies and their combination have been tested. The first one is to consider larger patches in the spirit of what proposed in [4] and the second one is to perform a second recovery on the recovered stresses. Some numerical tests in plane stress conditions are presented, showing the effectiveness of these procedures. Afterwards, a new recovery technique called Last Square Displacements (LSD) is introduced. This new procedure is based on last square interpolation of nodal displacements resulting from the finite element solution. In fact, it has been observed that the major part of the error affecting stress resultants is introduced when shape functions are derived in order to obtain strains components from displacements. This procedure shows to be ultraconvergent and is extremely cost effective, as it needs in input only nodal displacements directly coming from finite element solution, avoiding any other post-processing in order to obtain stress resultants using the traditional method. Numerical tests in plane stress conditions are than presented showing that the procedure is ultraconvergent and leads to convergent first and second order derivatives of stress resultants. In the end, transverse stress profiles reconstruction using First-order Shear Deformation Theory for laminated plates and three dimensional equilibrium equations is presented. It can be seen that accuracy of this reconstruction depends on accuracy of first and second derivatives of stress resultants, which is not guaranteed by most of available low order plate finite elements. RCP and LSD procedures are than used to compute convergent first and second order derivatives of stress resultants ensuring convergence of reconstructed transverse shear and normal stress profiles respectively. Numerical tests are presented and discussed showing the effectiveness of both procedures.

Edge-aware Graph Attention Networks: Joint Reasoning On Text and Knowledge Graphs for Biomedical Question Answering

Much of the real-world dataset, including textual data, can be represented using graph structures. The use of graphs to represent textual data has many advantages, mainly related to maintaining a more significant amount of information, such as the relationships between words and their types. In recent years, many neural network architectures have been proposed to deal with tasks on graphs. Many of them consider only node features, ignoring or not giving the proper relevance to relationships between them. However, in many node classification tasks, they play a fundamental role. This thesis aims to analyze the main GNNs, evaluate their advantages and disadvantages, propose an innovative solution considered as an extension of GAT, and apply them to a case study in the biomedical field. We propose the reference GNNs, implemented with methodologies later analyzed, and then applied to a question answering system in the biomedical field as a replacement for the pre-existing GNN. We attempt to obtain better results by using models that can accept as input both node and edge features. As shown later, our proposed models can beat the original solution and define the state-of-the-art for the task under analysis.

Gyrokinetic modelling of plasma transport and investigation on test particle dynamics

Turbulent plasmas inside tokamaks are modeled and studied using guiding center theory, applied to charged test particles, in a Hamiltonian framework. The equations of motion for the guiding center dynamics, under the conditions of a constant and uniform magnetic field and turbulent electrostatic field are derived by averaging over the fast gyroangle, for the first and second order in the guiding center potential, using invertible changes of coordinates such as Lie transforms. The equations of motion are then made dimensionless, exploiting temporal and spatial periodicities of the model chosen for the electrostatic potential. They are implemented numerically in Python. Fast Fourier Transform and its inverse are used. Improvements to the original Python scripts are made, notably the introduction of a power-law curve fitting to account for anomalous diffusion, the possibility to integrate the equations in two steps to save computational time by removing trapped trajectories, and the implementation of multicolored stroboscopic plots to distinguish between trapped and untrapped guiding centers. The post-processing of the results is made in MATLAB. The values and ranges of the parameters chosen for the simulations are selected based on numerous simulations used as feedback tools. In particular, a recurring value for the threshold to detect trapped trajectories is evidenced. Effects of the Larmor radius, the amplitude of the guiding center potential and the intensity of its second order term are studied by analyzing their diffusive regimes, their stroboscopic plots and the shape of guiding center potentials. The main result is the identification of cases anomalous diffusion depending on the values of the parameters (mostly the Larmor radius). The transitions between diffusive regimes are identified. The presence of highways for the super-diffusive trajectories are unveiled. The influence of the charge on these transitions from diffusive to ballistic behaviors is analyzed.

Computational design of a new type of sandwich cross-section for a defined solution of a tree-like column produced by wire-and-arc additive manufacturing

When it comes to designing a structure, architects and engineers want to join forces in order to create and build the most beautiful and efficient building. From finding new shapes and forms to optimizing the stability and the resistance, there is a constant link to be made between both professions. In architecture, there has always been a particular interest in creating new shapes and types of a structure inspired by many different fields, one of them being nature itself. In engineering, the selection of optimum has always dictated the way of thinking and designing structures. This mindset led through studies to the current best practices in construction. However, both disciplines were limited by the traditional manufacturing constraints at a certain point. Over the last decades, much progress was made from a technological point of view, allowing to go beyond today's manufacturing constraints. With the emergence of Wire-and-Arc Additive Manufacturing (WAAM) combined with Algorithmic-Aided Design (AAD), architects and engineers are offered new opportunities to merge architectural beauty and structural efficiency. Both technologies allow for exploring and building unusual and complex structural shapes in addition to a reduction of costs and environmental impacts. Through this study, the author wants to make use of previously mentioned technologies and assess their potential, first to design an aesthetically appreciated tree-like column with the idea of secondly proposing a new type of standardized and optimized sandwich cross-section to the construction industry. Parametric algorithms to model the dendriform column and the new sandwich cross-section are developed and presented in detail. A catalog draft of the latter and methods to establish it are then proposed and discussed. Finally, the buckling behavior of this latter is assessed considering standard steel and WAAM material properties.

Audiovisual materials and second-language acquisition: a comparison between native language subtitles and target language captions.

Over the last few years, the massive popularity of video streaming platforms has managed to impact our daily habits by making the watching of movies and TV shows one of the main activities of our free time. By providing a wide range of foreign language audiovisual content, these entertainment services may represent a powerful resource for language learners, as they provide them with the possibility to be exposed to authentic input. Moreover, research has shown the beneficial role of audiovisual textual aids such as native language subtitles and target language captions in enhancing language skills such as vocabulary and listening comprehension. The aim of this thesis is to analyze the existing literature on the subject of subtitled and captioned audiovisual materials used as a pedagogical tool for informal language learning.