This work deals with influence nanoparticles, as fillers of polymer, to electrical properties dielectric composite materials. Addition of just a few weight percent of nonofillers has profound impact on the physical, chemical, mechanical and electrical properties orf polymer. Simultaneously is focused on production and diagnostics by the relaxation spectroscopy and measure internal resistance. Examination material is epoxy resin TSA 220S filled Al2O3 and SiO2 nanoparticles.

Diploma thesis treat of effect of direct, alternate and pulse electrical stress on the properties surveyed electrical insulating material. Object of this experiment is crystalline high-density polystyrene QUINN PS. To monitor the stress is used the method of dielectric relaxation spectroscopy. Under examinations are the resultant dielectric spectra, which constitute the frequency dependencies of components of complex permitivity. Samples of the selected material are exposed to effects of alternate and pulse electrical stress on the different intensities of the electric field. In the direct field are then monitored absorption characteristics and specific volume resistance of the samples.

The dissertation deals with the time-domain dielectric relaxation spectroscopy of carboxymethylcellulose. The main attention was paid to the experimental part of research, mainly to the design and subsequent development of an experimental setup for the measurement of discharge currents and for their processing and analysis. The subject of the measurement is carboxymethylcellulose (CMC), which is a simple polysaccharide used in wide range of applications, among else also in biomedical engineering. The study of CMC properties has required the development of a new experimental set-up of original design, which includes the equilibration (short-circuiting) of a sample before the measurement, charging and discharging at defined time intervals, switching between these two modes, recording of measurement, adjustments and processing of measured signals up to Fourier transformation into the frequency domain and, finally, calculation of complex permittivity of the sample. The frequency dependence of complex permittivity or its imaginary part, obtained by Fourier transformation of discharge current in time domain, is then referred to as the dielectric spectrum. In view of the fact that current measurements were done at very low levels of measured signal (below 10-12 A) the whole measurement was no easy matter. The framework of the work also necessitated studies and subsequent resolution of problems associated with shielding, grounding, presence of noise and sensitivity to various ambient influences. The research work focused on a reliable and trustworthy measurement of very low discharge currents and, subsequently, mathematical processing of noise present in them, i.e., operations with the original, experimentally established signal in time domain, leading in principle to a digital filtration of measured dielectric data. A further pursued objective is the explanation of dielectric parameters of tested carboxymethylcellulose sample in the widest possible frequency spectrum. The integral part of the research was the selection and application of the method for the transformation of the adjusted signal to the frequency domain. The experimental works, including data processing, were carried out in the Department of Physics, Brno FEEC BUT. Measurements were done with Keithley 617 Electrometer, HP4284A Frequency Analyzer and Janis CCS-400-204 cryogenic system. The results were completed with results obtained at the V Department of Experimental Physics, Centre for Electronic Correlations and Magnetism, University of Augsburg, Germany.

Dans le cadre de cette thèse, nous avons réalisé l’étude de systèmes amorphes moléculaires chiraux en évaluant leur vieillissement, leur mobilité ainsi que leur capacité à recristalliser en fonction de la composition énantiomérique du matériau. Pour limiter les facteurs additionnels à la chiralité, ce travail s’est concentré sur des systèmes modèles formant des conglomérats stables : N-acetyl-α-methylbenzylamine (Nac-MBA) et 5-ethyl-5-methylhydantoin (12H). De ces travaux il ressort que l’impact le plus spectaculaire de la chiralité est exprimé dans la propension à la cristallisation ou l’habilité à former un verre (qui augmente de façon inversement proportionnelle de l’excès enantiomérique (ee)). Les cinétiques de vieillissement sont implicitement impactées par l’ee : Celles-ci sont plus lentes pour les ee importants. Enfin, il semble que les processus de relaxation ainsi que les temps associés soient identiques quelle que soit l’ee, bien que le comportement à la cristallisation soit lui significativement impacté. A noter que la signature la plus manifeste de la chiralité dans l’état amorphe du Nac-MBA s’exprime dans l’intensité diélectrique des processus D et α. / In the framework of this thesis, we carried out the study of amorphous chiral molecular systems by evaluating their molecular mobility, the evolution of physical properties during aging and the recrystallization behavior as function of the initial enantiomeric excess (ee). In order to avoid factors additional to chirality itself, we focused on enantiomeric systems forming stable conglomerates (full chiral discrimination in the solid state) by choosing two model compounds: 5-ethy-5-methylhydantoin (12H) and N-acetyl-α-methylbenzylamine (Nac-MBA). From this thesis it was shown that the most spectacular effects of chirality in the amorphous state is expressed in the GFA or the crystallization propensity. The GFA increases as the ee decreases. The kinetics of physical aging is implicitly impacted by chirality. Glassy pure enantiomer requires more time to reach equilibrium than that of an intermediate composition. This situation is hypothetically due to constraints effects mostly resulting from a strong nucleation behavior in the glass state at high ee. Furthermore, the time scale of all the processes (D, α, βJG, γ) and the evolution of their temperature dependency are approximatively identical even though the crystallization behavior is highly impacted by ee. it seems that molecular mobility would not be a key parameter in the crystallization behavior of Nac-MBA. The main expression of chirality in amorphous Nac-MBA is evidenced in the signature of the dielectric strength of both D and α processes.

The present thesis deals in detail the influence of solvent dynamics and solvation on ion transport in succinonitrile based plastic crystalline electrolytes. The main objective of correlating plastic solvent characteristics with ion transport was achieved by probing the electrolyte using characterization techniques at various length and time scales. Although majority of the results presented in this thesis focus on a prototype succinonitrile electrolyte (succinonitrile-lithium perchlorate, SN-LiClO4), the conclusions drawn from the results on SN-LiClO4 are quite general and can be extended to various types of salts as well as plastic crystalline matrices. Chapters 2-5 demonstrate in a systematic and detailed manner the beneficial influence of solvent dynamics on ion transport in the solid state. The thesis comprises of six chapters. A brief discussion of the contents and highlights of the individual chapters are described below: Chapter 1 briefly reviews the importance of various types of electrolytes for electrochemical applications. The chapter starts with a discussion on different types of liquid and solid crystalline electrolytes and their drawbacks in electrochemical devices such as lithium-ion batteries. Following the discussion on the two extremes of electrolytes viz. liquid and solid electrolytes, various soft matter electrolytes including polymer and plastic crystalline materials are discussed. Aims of the thesis are specified in chapter 1. Chapter 2 discusses plastic crystalline electrolytes as prospective electrolytes for electrochemical applications. In this chapter, we present a detailed study of correlation of ion transport with solvent structure and dynamics in lithium perchlorate (LiClO4)-succinonitrile (SN), a prototype succinonitrile based plastic crystalline electrolyte. Significant influences of the salt on the crystallographic structure, trans-gauche isomerism and solvation properties of succinonitrile (SN) are observed. Ionic conductivity (ac-impedance spectroscopy) and single crystal X-ray studies (in-situ cryo crystallography) reveal the influence of configurational isomerism and ion solvation on ion transport in LiClO4-SN. We quantify the ion association using theoretical analysis of Fuoss-Onsager formalism for various LiX-SN (typically X = ClO4-, CF3SO3-, TFSI-) electrolytes. Thermal (differential scanning caloriemetry) and spectroscopic (Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (NMR)) studies have also been discussed in the chapter to support our proposition. Chapter 3 describes our investigation on issues other than salt that are likely to affect ion transport in Li-salt-SN based plastic crystalline electrolytes such as water in sample and sample thermal history. We investigate here in a detailed manner the influence of water and thermal history on SN configurational isomerism and solvation in LiClO4-SN. LiClO4 in SN electrolyte samples were prepared in various ways for the fulfillment of the objectives of the study of the present chapter. Correlation of water and thermal history on ion transport were studied via ac-impedance spectroscopy and room temperature Fourier transform infrared (FTIR) spectroscopy. The ionic conductivity and infra-red findings were supplemented via differential scanning calorimetry (DSC). Chapter 4 presents dielectric relaxation spectroscopy (DRS) to study the various relaxation processes of the plastic crystalline solvent and ionic species responsible for ion-transport in succinonitrile-based electrolytes. For the DRS study, we select the same system i.e. SN-LiClO4 for which the role of solvent dynamics and ion-association on ion transport was discussed in detail in chapter 2. We supplement the ionic conductivity and various spectroscopic investigations highlighted in chapter 2 via study of the frequency dependence of dielectric function. The permittivity data are further analyzed using Havriliak-Negami (HN) and Kohlrausch-Williams-Watta (KWW) functions for identification of various processes and also for detailed insight on the ion transport mechanism. Chapter 5 comprises of the temperature dependence the bulk acoustic phonons in SN and SN-LiX (X = ClO4-, CF3SO3-, TFSI-, Cl-) electrolytes from (200-300) K. Room temperature Brillouin spectra of SN based plastic crystalline electrolytes with different cationic salts (MClO4-, M = Li+, Na+, Rb+) were also measured. The influences of salt concentration and temperature on solvent dynamics and ion-association effect have been investigated in detail for the SN-LiClO4 electrolyte. The Brillouin data were further analyzed using Lorentzian and Fano resonance function for identification of behavior of various Brillouin modes. An attempt was made to understand ion transport mechanism in SN-LiX plastic crystalline electrolytes based on the concept of molecular liquids as opposed to conventional solid state defect chemistry. The chapter also discusses preliminary results on the relaxational dynamics of SN and SN-LiClO4 in the plastic phase examined using quasi elastic neutron scattering (QENS) facility at ILL-Grenoble IN16 beamline. Chapter 6 provides a brief summary of the work presented in the thesis and discusses how knowledge from the present work (chapters 2-5) can be utilized to generate new electrolytes. The system proposed is a liquid electrolyte based on bis-nitrile (G0-CN) which does not possess majority of the detrimental issues associate with conventional liquids and various improvisations of polymer electrolytes. We also show that the various dendrimer generations obtained from the monomer bis-nitrile (G0-CN) can also be utilized as an alternative solvent for generation of liquid electrolytes for electrochemical devices such as (primary/secondary) batteries. In a way, we discuss a novel liquid electrolyte system whose physical (viscosity, dielectric constant) and solvation properties can be tuned easily to fulfill task of specific objectives. The preliminary ionic conductivity, viscosity and electrochemical studies of the Gn-CN-Li-salt (n=0-2) liquid electrolytes show considerable promise. Though the prospective dendrimer solvent is a liquid, we envisage that in future compounds with similar chemical properties can also be synthesized in the soft matter state.

L’originalité de ce travail repose sur une approche physique et physico-chimique des propriétés de mélanges de polylactides de chiralité différentes (poly L-lactique acide et poly D-lactique acide) et sur l’influence de cette chiralité sur les propriétés des phases amorphes de ces matériaux. Les matériaux sont des mélanges élaborés à partir de deux homopolymères (PLLA et PDLA) selon deux méthodes ; coulée en solution ou par extrusion. Nous avons étudié des matériaux totalement amorphes et cristallisés de façon isotrope afin de générer une phase amorphe plus ou moins confinée. Il est montré que le mélange pouvant donner naissance à une phase cristalline stéréocomplexe ne peut être obtenu que dans certaines conditions. Les résultats des analyses thermiques et de perméation ont montré que le mélange PLLA/PDLA améliore certaines propriétés du matériau, notamment des propriétés barrières à l’eau et aux gaz plus élevées par rapport aux homopolymères parents. Afin d’étudier la mobilité moléculaire des phases amorphes, du vieillissement physique et de la relaxation structural (relaxation α et β), le concept de Région de Réarrangement Coopératif (CRR) a été appliqué. Il a été montré que les phases amorphes des homopolymères et du mélange ont exactement les mêmes propriétés à la transition vitreuse et dans l’état vitreux lorsque les matériaux sont totalement amorphes. / The originality of this work is based on analysis of physical and physicochemical properties of polylactide mixtures of different chirality (poly L-lactic acid and poly D-lactic acid) and on the influence of the chirality on the amorphous phase’s properties. The materials mixtures are elaborated from two homopolymers (PLLA and PDLA) according to two methods; solution casting or extrusion. Totally amorphous and isotropically crystallized materials with more or less confined amorphous phase were studied. It is shown that a stereocomplex crystalline phase can be obtained only under certain experimental conditions. The results of the thermal and permeation analyzes showed that the PLLA / PDLA mixture improved certain properties of the material, namely higher barrier properties towards liquid water and gases were obtained compared to parent homopolymers. In order to study the molecular mobility of amorphous phases, physical aging and structural relaxation (α and β relaxation), the Cooperative Rearrangement Region (CRR) concept has been applied. It has been shown that the amorphous phases of the homopolymers and the mixture have exactly the same properties at the glass transition and in the vitreous state when the materials are totally amorphous.

No description available.

Diese Arbeit untersucht die Photo-Lumineszenz (PL)-Unterbrechung (Blinken) einzelner in Polymer-Nanopartikeln eingebetteter CdSe/CdS Halbleiter-Nanokristalle (Quantenpunkte) im Einfluss elektrischer Gleich- und Wechselfelder mittels Weitfeld-Mikroskopie. Hierbei emittieren die einzelnen Quantenpunkte trotz kontinuierlicher Anregung mit einer zwischen hellen An- und dunklen Aus-Zuständen variierenden PL-Intensität. Die Ergebnisse zeigen, dass die Dynamik dieses Blinkens durch Wechselfelder stark beeinflusst wird und von deren Feldstärke, teilweise auch deren Feldfrequenz abhängt. Für zunehmende Feldstärken lässt sich ein schnellerer Wechsel zwischen An- und Aus-Zuständen (erhöhte Blinkfrequenz) beobachten, der von einer reduzierten Häufigkeit langer An- und Aus-Ereignisse begleitet wird. Der Verlauf der An-Zeit-Verteilungen bei kleinen Zeiten wird zunehmend (monoton) flacher, während die Verteilungen der Aus-Zeiten zunächst ebenfalls einem analogen Trend folgen, ab einer bestimmten und von der Feldfrequenz abhängenden Feldstärke jedoch wieder steiler verlaufen. Ein solcher Monotonie-Wechsel in der Blinkdynamik im Fall einer gleichbleibenden Variation einer äußeren Bedingung wurde bei Halbleiter-Nanokristallen so erstmalig beobachtet. Für Gleichfelder zeigen sich hingegen nahezu keine Auswirkungen. Lediglich die An-Zeit-Verteilungen sowie die Blinkfrequenz im Fall hoher Feldstärken werden modifiziert. Die Ergebnisse werden im Kontext verschiedener aktueller Modelle zur PL-Unterbrechung wie dem trapping-Modell, dem self-trapping-Mechanismus oder dem Modell multipler Rekombinationszentren diskutiert und diese entsprechend erweitert. Dabei stehen die dielektrischen Eigenschaften und die Relaxationsdynamik der lokalen Quantenpunkt-Umgebung im Mittelpunkt, deren Reaktion auf die externen Felder durch eine zeitabhängige Ausrichtung permanenter Dipole beschrieben werden kann.

The dissertation thesis deals with the analysis of prospective environmentally compatible electrical insulating fluids for electrical engineering in relation to their chemical structure. The thesis starts with the overview of the current state of the art and of the latest trends in the use of synthetic and biodegradable natural oils. In the experimental part were studied these oils: mineral oils, rapeseed oil, sunflower oils, soybean oil, methyl oleate, peanut oil, MCT oil, castor oil and other. Dielectric properties were measured using LRC meter Agilent 4980A including dielectric liquid test fixture Agilent 16452A and also by the Novocontrol Alpha-A analyzer. Electrical properties are presented in the frequency range 10 mHz – 1 MHz range in the temperature interval 253 K to 363 K. The work goes on with the study of the suitability of individual oils for lower temperature, including the impact of the chemical structure and formulation on electrical properties.

Diese Arbeit untersucht die Photo-Lumineszenz (PL)-Unterbrechung (Blinken) einzelner in Polymer-Nanopartikeln eingebetteter CdSe/CdS Halbleiter-Nanokristalle (Quantenpunkte) im Einfluss elektrischer Gleich- und Wechselfelder mittels Weitfeld-Mikroskopie. Hierbei emittieren die einzelnen Quantenpunkte trotz kontinuierlicher Anregung mit einer zwischen hellen An- und dunklen Aus-Zuständen variierenden PL-Intensität. Die Ergebnisse zeigen, dass die Dynamik dieses Blinkens durch Wechselfelder stark beeinflusst wird und von deren Feldstärke, teilweise auch deren Feldfrequenz abhängt. Für zunehmende Feldstärken lässt sich ein schnellerer Wechsel zwischen An- und Aus-Zuständen (erhöhte Blinkfrequenz) beobachten, der von einer reduzierten Häufigkeit langer An- und Aus-Ereignisse begleitet wird. Der Verlauf der An-Zeit-Verteilungen bei kleinen Zeiten wird zunehmend (monoton) flacher, während die Verteilungen der Aus-Zeiten zunächst ebenfalls einem analogen Trend folgen, ab einer bestimmten und von der Feldfrequenz abhängenden Feldstärke jedoch wieder steiler verlaufen. Ein solcher Monotonie-Wechsel in der Blinkdynamik im Fall einer gleichbleibenden Variation einer äußeren Bedingung wurde bei Halbleiter-Nanokristallen so erstmalig beobachtet. Für Gleichfelder zeigen sich hingegen nahezu keine Auswirkungen. Lediglich die An-Zeit-Verteilungen sowie die Blinkfrequenz im Fall hoher Feldstärken werden modifiziert. Die Ergebnisse werden im Kontext verschiedener aktueller Modelle zur PL-Unterbrechung wie dem trapping-Modell, dem self-trapping-Mechanismus oder dem Modell multipler Rekombinationszentren diskutiert und diese entsprechend erweitert. Dabei stehen die dielektrischen Eigenschaften und die Relaxationsdynamik der lokalen Quantenpunkt-Umgebung im Mittelpunkt, deren Reaktion auf die externen Felder durch eine zeitabhängige Ausrichtung permanenter Dipole beschrieben werden kann.