The dissertation thesis submitted deals with the study of dielectric properties of epoxy nanocomposites containing nanoparticles of inorganic oxides. These nanocomposites may have a promising technologic application for electric insulations in view of their higher resistance against partial discharges; yet information about their behavior in the course of ageing is not available. If at least a partial mass replacement of the currently used epoxy insulation with nanocomposite-based insulations is due to occur, the knowledge of the changes of their dielectric properties in the course of their operation will become indispensable. Within the framework of this dissertation, ensembles of samples of epoxy resins without fillers and with Al2O3, WO3, TiO2 and SiO2 fillers in the form of nanopowders, in concentrations up to 12 wt %, have been prepared. These ensembles have been measured prior to ageing and exposed to long-time (up to 5000 hours) ageing at increased temperatures 200, 250 and 300 °C and in a few cases also at 330 and 360 °C. Samples were measured in the course of ageing roughly in a logarithmic time series after 1, 2, 5, 10, 20, 50, 100, 200, 500, 1000, 2000 and 5000 hours. The measured quantities included complex permittivity , internal resistivity i and loss factor tan at temperatures ranging from -153 °C to +167 °C and in the frequency range 10-2 – 106 Hz. Changes in nanocomposites have been investigated using not just dielectric spectroscopy measurements, but other methods, too, namely Fourier-transformed infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). The experiments have proved that materials with different fillers respond to the same concentrations of various fillers in different ways. The addition of nanoparticles, without the addition of microparticles, at a relatively low concentration (max 12 wt %), was not sufficient for reaching fundamental changes in dielectric spectrum; only smaller changes of dielectric strength and shifts of relaxations and in relaxation maps have occurred. Out of more pronounced changes, increase of concentration of the SiO2 filler in the epoxy matrix brings about a decrease of electrical conductivity in the resulting nanocomposite. The TiO2 filler had a different impact. Different TiO2 concentrations make their marked appearance in the region between the relaxation and relaxation. The TiO2-filled nanocomposites do not exhibit the unambiguous dependence of electrical conductivity on nanofiller concentration. It can be concluded that the mere addition of nanoparticles, without the addition of established microparticles, does not change the dielectric spectrum substantially. Generally, a serious problem was the production of the nanocomposite with a uniform distribution of nanoparticles. The preparation of such a nanocomposite was not trivial and, in industrial applications, this issue will require a specific focus, so as to avoid the formation of undesirable aggregates. Within the framework of this research, a methodology for the production of an epoxy nanocomposite has been developed with as high as possible uniformity of nanoparticle distribution.

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Les Pérovskites hybrides organique-inorganique (PHOIs) ont suscité d’intenses recherches au coursdes dernières années. Dans cette thèse, nous avons dans un premier temps mis au point les différentsprocessus de préparation des échantillons et réalisé une caractérisation complète des films parmicroscopie à force atomique, spectroscopie photo-électronique par rayons X, mesure du potentiel desurface par sonde de Kelvin et mesure de la mobilité des charges par temps de vol. La distribution despièges à l'interface PHOI/Au a été étudiée via des mesure J-V-L en fonction de la températurecombinées avec des simulations numériques. Les relaxations diélectriques dans les PHOIs, tels que lamigration des ions et l’orientation du dipôle du cation organique, ont été étudiés par spectroscopied’impédance en fonction de la température. Dans la dernière partie de cette thèse, nous présentons uneétude originale qui démontre un mouvement des protons du groupement ammonium des cationsorganiques à l’interface avec le PEDOT : PSS. / Hybrid-organic-inorganic perovskites (HOIPs) have provoked intense research over the recent years.In this thesis, we contribute to this investigation by first examining the results of different solutionpreparation processes, followed by characterizing the films using atomic force microscopy, X-raydiffraction, ultra-violet photoelectron spectroscopy, X-ray photoelectron spectroscopy, Kelvin probesurface potential measurement, and time-of-flight mobility measurement. The state distribution of theHOIP/Au interface was then studied by low temperature J–V–L measurement combined withnumerical simulation. In the process of these characterizations, it became clear that the dielectricrelaxations in HOIPs, such as ion migration and organic cation dipole orientation, play an importantrole in the material, and the next part of the thesis presents an analysis of these mechanisms with thehelp of temperature dependent impedance spectroscopy measurement. These studies built thefoundations for the final part of the thesis, where we investigated a so far elusive subject in HOIPs, themigration of protons

This doctoral thesis deals with the analysis of dielectric spectra of glycerol with dielectric relaxation spectroscopy (DRS). Dielectric spectra of glycerol have been measured in the frequency range 20 Hz to 10 MHz and in the temperature range 10 K to 300 K. The observed dielectric spectra featured a typical relaxation maximum, which could be in the first approximation described by the Arrhenius equation. The activation energy of the relaxation process observed was 90 MJ/kmol. The relaxation strength as well as the shape of the relaxation peak remained in the temperature interval 180 K - 230 K (visibility of peak) almost the same, thus indicating that no change of the relaxation mechanism comes about. Much attention was in the thesis paid to the analysis of the excess component of the relaxation alfa process, in the literature commonly denoted as "excess wing". The thesis puts forward a procedure for the quantification of the magnitude of the excess wing. The excess wing magnitude thus determined turns out to increase monotonously with increasing temperature. The excess wing is here interpreted as a manifestation of a weakly-pronounced beta relaxation.

L'objectif principal de cette thèse est de mettre en évidence l'effet de la méthode de préparation sur la dynamique de relaxation des polymères en films minces. Nous nous sommes focalisés en particulier sur l'importance de la maîtrise du taux d'évaporation du solvant lors de la préparation des films, en termes de contrôle de la magnitude des contraintes résiduelles et les conséquences engendrées sur les propriétés physiques. Dans un premier temps, nous exposons la problématique de déviation des propriétés de polymères en films minces et le lien avec la technique de préparation. Nous décrivons un moyen simple permettant de contrôler le taux d'évaporation du solvant en ajustant la concentration de la solution et la vitesse de rotation de la tournette. Les expériences de démouillage nous ont permis de suivre l'effet du taux d'évaporation du solvant sur les propriétés viscoélastiques des polymères près de la Tg. Les résultats obtenus sur des films minces de polystyrène mettent en évidence le rôle de la méthode de préparation sur la probabilité de rupture des films, les temps caractéristiques de relaxation, la dynamique de démouillage et la magnitude des contraintes résiduelles. Dans une seconde partie, nous présentons également une expérience basée sur la propagation des fissures dans les films minces vitreux. Une simple observation microscopique, ainsi que des imageries en AFM permettent de prouver le rôle du taux d'évaporation du solvant lors de la préparation. Enfin, nous explorons une nouvelle approche expérimentale portant sur la possibilité d'investigations en temps réel et lors de démouillage la relaxation moléculaire des chaînes dans les films minces par des mesures diélectriques directes. Nous avons réussi à prouver non seulement un rôle de la méthode de préparation des films mais également que la restauration du comportement du polymère en volume « bulk » est possible en fonction du temps quelques soient les paramètres du film. Nous confirmons ainsi que les propriétés anormales observées dans les films minces spin-coatés sont dictées par l'état métastable provoqué par la méthode de préparation / The aim of this work is to highlight the influence of the sample preparation on the relaxation dynamics of supported polymer thin films. We focus in particular on the importance of tuning the solvent evaporation rate during films preparation, in terms of controlling the magnitude of residual stresses, and the impact on the physical properties. Firstly, we expose the deviation of the polymer behavior in thin polymer films related to the preparation technique. Then, we describe how the solvent evaporation rate can be precisely tuned by varying the concentration of the solution and the rotation rate of the spin coater. Dewetting experiments allowed us to investigate the effect of the solvent evaporation rate on the viscoelastic behavior of the polymers near the Tg. The probability of films rupture, the characteristic time, dewetting dynamics and the magnitude of residual stresses are deduced to prove the impact of sample preparation. In the second part, we present cracks propagation experiments in glassy thin films. A simple microscopic observation, as well as AFM imaging are used to emphasize the role of the solvent evaporation rate during the preparation. Finally, we present a new experimental approach to investigate in real time and during dewetting the dynamics of polymers in thin films by direct dielectric measurements. We have successfully proved not only the impact of sample preparation but also the restoration of the bulk behavior of polymers is possible during the time whatever the film parameters. We therefore confirm that the anomalous properties observed in spin-coated films are governed by the metastable state induced by the sample preparation

A resonant microwave cavity technique was employed to study the dielectric behavior of some polar and non-polar liquids near the phase transition temperatures at microwave frequencies of 7.2, 9.2 and 10.1 GHz. The Slater perturbation equations for a resonant microwave cavity are briefly discussed to show that the above technique can be used to determine both the real and imaginary parts of dielectric response. Abrupt changes in dielectric response were observed near the phase transition temperatures for the polar liquids studied in this investigation. The dielectric relaxation phenomenon in liquids has been treated as a chemical rate process and the abrupt change in the dielectric response of the liquids near phase transition temperatures is shown to be related to the dramatic changes in the free energy of activation of the molecules. Some values of the free energy of activation were deduced for the various compounds from data obtained in this investigation.

As células eletroquímicas emissoras de luz (PLECs) pertencem a um novo ramo importante na optoeletrônica orgânica devido ao seu grande potencial para ser usado como ponto - pixels para telas coloridas e também para painéis de iluminação. Diferentemente de diodos orgânicos emissores de luz (OLEDs), a tecnologia de OLECs ainda está em estágios iniciais de desenvolvimento, em comparação com a tecnologia de OLED , OLECs tem a vantagem de ser operado em ambas as polaridades de tensão ( para a frente ou de polarização reversa ), e, além disso, o seu desempenho é menos dependente dos materiais do eletrodos e a espessura da camada ativa do dispositivo. A camada ativa de um OLEC compreende uma mistura de um polímero eletroluminescente conjugado e um eletrólito de polímero. Consequentemente, o transporte elétrico durante a operação do dispositivo envolve uma combinação de dinâmica iônica e eletrônica e efeitos intrincados nas interfaces com os eletrodos. A literatura apresenta até agora duas abordagens diferentes para descrever o fenômeno de transporte nas OLECs. O modelo de eletrodinâmica, que combina separação iônica com o processo de difusão limitada eletrônica, e o modelo de dopagem eletroquímico que considera uma dopagem eletroquímica do polímero conjugado, dando a formação de uma junção p-i-n na camada ativa. Usando as medidas de decaimento da corrente sobre uma voltagem aplicada e espectroscopia de impedância /admissão , investigamos o transporte de portadores de carga em um OLEC tendo como camada ativa uma mistura de poli [ ( 9, 9 - dioctyl - 2, 7 - divinileno - fluorenileno ) - alt - co - { 2 - metoxi -5 - ( 2 - etil- hexiloxi ) -1,4 - fenileno } ] ( PFGE ) , com poli ( óxido de etileno ) ( PEO ) complexado com triflato de lítio ( TriLi ) , na proporção 01:01 : X , onde X foi de 0,10 , 0,05 , 0,01 , 0,00. Foram obtidos dados importantes relacionados com efeito iônico e eletrônico durante a operação deste PLEC, sendo que as medidas de transiente e de impedância mostraram que o movimento iônico auxilia o processo de injeção eletrônica. Outro fato relevante é que o desempenho da PLEC é dependente da formação da dupla camada iônica que tem sua espessura abaixo de 10 nm e que o processo de sua formação depende altamente da condução iônica, que por sua vez vai depender da quantidade de íons e de sua mobilidade, sendo influenciando por fatores como concentração de sal e temperatura do dispositivo. As medidas realizadas mostram que as PLECs com 2,5 e 5% de concentração de sal apresentam o melhor desempenho. / Organic Light-emitting Electrochemical Devices (OLECs) belong to a new important branch in organic optoelectronics due to their great potential to be used as dot-pixels for color displays and also to lighting panels. Differently from organic light-emitting diodes (OLEDs), the technology of OLECs is still in early stages of development. In comparison to OLED technology, OLECs have the advantage in being operated in both voltage polarities (forward or reverse bias), and, in addition, their performance is less dependent on the electrode materials and the device thickness. The active layer of an OLEC comprises a mixture of a conjugated electroluminescent polymer and a polymer electrolyte. Consequently, the electrical transport during the device operation involves a combination of ionic and electronic dynamics and intricate effects at the interfaces with the electrodes. The literature presents so far two different approaches to describe the transport phenomenon in the OLECs. The electrodynamic model, which combines ionic charge separation with electronic diffusionlimited process, and the electrochemical doping model that consider an electrochemical doping of the conjugated polymer, giving and the formation of a p-i-n junction in the active layer. Using current decay under an applied voltage measurements and impedance/admittance spectroscopy, we investigate charge carrier transport in an OLEC having as active layer a mixture of poly [(9, 9 - dioctyl - 2, 7 - divinileno - fluorenileno) - alt - co - {2 - methoxy -5 - (2 - ethyl-hexyloxy) -1,4 - phenylene}] (PFGE), with poly (ethylene oxide) (PEO) complexed with lithium triflate (TriLi), in the proportion 1:1:X, where X was 0.10, 0.05, 0.01, 0.00. We have obtained important results related to ionic and electronic effect during this operation PLEC. This measurements of transient current and impedance showed that ionic movement aids the process of electron injection. Another relevant fact is that the performance of PLEC is dependent on the formation of ionic double layer having thickness below 10 nm. The formation of this double layers is highly dependent on the ionic conduction, which in turn will depend on the amount of ions. The ionic mobility is influenced by factors such as salt concentration and temperature of the device. The measurements show that PLECS with 2.5 and 5% salt concentration had the best perform.

Ceramic-matrix composites of alumina and silicon carbide whiskers have recently found novel commercial application as electromagnetic absorbers. However, a detailed understanding of how materials issues influence the composite electrical response, which underpins this application, has been absent until now. In this project, such composites were electrically measured over a wide range of conditions and modeled in terms of various aspects of the microstructure in order to understand how they work. For this purpose, three types of composites were made by different methods from the same set of ceramic powder blends loaded with different volume fractions of whiskers. In doing so, the interfaces between whiskers, the preferred orientations of whiskers, and the structure of electrically-connected whisker clusters were varied; the whisker aspect-ratio distributions were the same for all methods. At the electrode interfaces, Schottky barriers at the junctions of the electrically-percolating wide-bandgap semiconductor whiskers on the surface were responsible for a significant portion of the total measured impedance. The associated electrical response was studied on the microscopic and macroscopic level, and the gap between these different scales was bridged. Also, a modeling approach was developed for the non-linear behavior of the composite which results from these barriers. In regards to the whiskers within the composite bulk, the effects of various factors on the wide-band frequency dependence of the dielectric response and dc conductivity were explained and contextualized for the electromagnetic absorber application. Such factors include whisker preferred orientation, electrical percolation and cluster structure, the interfaces between electrically-connected SiC whiskers, and porosity. A quantitative correlation between the anisotropy of the microstructure and that of the conductivity was found, and was understood in terms of the interfacial SiC-Al2O3-SiC conduction mechanism. This behavior was shown to differ from the behavior commonly observed for other disordered mixtures of relatively conductive particles dispersed inside insulating polymer hosts. A description of this new mechanism was developed based on an observed correlation between the temperature dependencies of the static and radio-frequency electrical responses. Also, the aforementioned non-linear response model was expanded upon to describe conduction through and across electrically-percolated clusters. The model demonstrates how loading and interface behavior influence the topology and the strength of the non-linear response of the clusters.