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.

Sintesi e caratterizzazione di polimeri per l’ottica non lineare

L'osservazione di diversi fenomeni ottici come la generazione della seconda o della terza armonica (generazione di luce con frequenza raddoppiata (SHG) o generazione di luce con frequenza triplicata (THG)) quando un materiale interagisce con una sorgente ad alta intensità, ha portato ad un crescente interesse per le proprietà ottiche non lineari (NLO). Questi ed altri fenomeni ottici non lineari potrebbero essere impiegati per aumentare le prestazioni dei dispositivi optoelettronici e fornire soluzioni per progettare nuovi metamateriali funzionali. L'impiego di sistemi polimerici contenenti gruppi funzionali con caratteristiche NLO rappresenta una sfida per migliorare tali proprietà e la loro lavorabilità. In questo lavoro, è stata sviluppata una strategia sintetica per ottenere un cromoforo con struttura donatore-accettore-donatore (D-A-D), dove la simmetria dei dipoli (push-pull-push) può potenzialmente fornire proprietà NLO del terzo ordine. Attraverso una sintesi multistep è stato sintetizzato il monomero a base metacrilica con il cromoforo NLO, successivamente copolimerizzato con lo stirene per aumentare la lavorabilità del polimero. Il polimero ed il monomero saranno impiegati per preparare cristalli fotonici. Inoltre, verrà effettuata un'ampia caratterizzazione per approfondire le proprietà ottiche e quindi per ottimizzare i dispositivi finali.

Ray-tracing assessment of the robustness of Physical Layer Security key generation protocol

Nowadays, information security is a very important topic. In particular, wireless networks are experiencing an ongoing widespread diffusion, also thanks the increasing number of Internet Of Things devices, which generate and transmit a lot of data: protecting wireless communications is of fundamental importance, possibly through an easy but secure method. Physical Layer Security is an umbrella of techniques that leverages the characteristic of the wireless channel to generate security for the transmission. In particular, the Physical Layer based-Key generation aims at allowing two users to generate a random symmetric keys in an autonomous way, hence without the aid of a trusted third entity. Physical Layer based-Key generation relies on observations of the wireless channel, from which harvesting entropy: however, an attacker might possesses a channel simulator, for example a Ray Tracing simulator, to replicate the channel between the legitimate users, in order to guess the secret key and break the security of the communication. This thesis work is focused on the possibility to carry out a so called Ray Tracing attack: the method utilized for the assessment consist of a set of channel measurements, in different channel conditions, that are then compared with the simulated channel from the ray tracing, to compute the mutual information between the measurements and simulations. Furthermore, it is also presented the possibility of using the Ray Tracing as a tool to evaluate the impact of channel parameters (e.g. the bandwidth or the directivity of the antenna) on the Physical Layer based-Key generation. The measurements have been carried out at the Barkhausen Institut gGmbH in Dresden (GE), in the framework of the existing cooperation agreement between BI and the Dept. of Electrical, Electronics and Information Engineering "G. Marconi" (DEI) at the University of Bologna.

WEC-Sim Application for the Assessment of Wave Energy Generation in the Tyrrhenian Sea and the North Sea Through the 2-Body Point Absorber (2BPA) and the Oscillating Surge Wave Energy Converter (OSWEC)

In recent years, developed countries have turned their attention to clean and renewable energy, such as wind energy and wave energy that can be converted to electrical power. Companies and academic groups worldwide are investigating several wave energy ideas today. Accordingly, this thesis studies the numerical simulation of the dynamic response of the wave energy converters (WECs) subjected to the ocean waves. This study considers a two-body point absorber (2BPA) and an oscillating surge wave energy converter (OSWEC). The first aim is to mesh the bodies of the earlier mentioned WECs to calculate their hydrostatic properties using axiMesh.m and Mesh.m functions provided by NEMOH. The second aim is to calculate the first-order hydrodynamic coefficients of the WECs using the NEMOH BEM solver and to study the ability of this method to eliminate irregular frequencies. The third is to generate a *.h5 file for 2BPA and OSWEC devices, in which all the hydrodynamic data are included. The BEMIO, a pre-and post-processing tool developed by WEC-Sim, is used in this study to create *.h5 files. The primary and final goal is to run the wave energy converter Simulator (WEC-Sim) to simulate the dynamic responses of WECs studied in this thesis and estimate their power performance at different sites located in the Mediterranean Sea and the North Sea. The hydrodynamic data obtained by the NEMOH BEM solver for the 2BPA and OSWEC devices studied in this thesis is imported to WEC-Sim using BEMIO. Lastly, the power matrices and annual energy production (AEP) of WECs are estimated for different sites located in the Sea of Sicily, Sea of Sardinia, Adriatic Sea, Tyrrhenian Sea, and the North Sea. To this end, the NEMOH and WEC-Sim are still the most practical tools to estimate the power generation of WECs numerically.

Latent representations for traditional music analysis and generation

We create and study a generative model for Irish traditional music based on Variational Autoencoders and analyze the learned latent space trying to find musically significant correlations in the latent codes' distributions in order to perform musical analysis on data. We train two kinds of models: one trained on a dataset of Irish folk melodies, one trained on bars extrapolated from the melodies dataset, each one in five variations of increasing size. We conduct the following experiments: we inspect the latent space of tunes and bars in relation to key, time signature, and estimated harmonic function of bars; we search for links between tunes in a particular style (i.e. "reels'") and their positioning in latent space relative to other tunes; we compute distances between embedded bars in a tune to gain insight into the model's understanding of the similarity between bars. Finally, we show and evaluate generative examples. We find that the learned latent space does not explicitly encode musical information and is thus unusable for musical analysis of data, while generative results are generally good and not strictly dependent on the musical coherence of the model's internal representation.