O presente estudo versa sobre a proposição ou extensão de modelos simples para descrever os seguintes fenômenos envolvendo agregados anfifílicos: i-) Influência de sal na concentração micelar crítica (CMC) e número médio de agregação () de micelas zwitteriônicas. ii-) Influência da interação eletrostática (neste caso, repulsiva) e tamanho de \"domínios\" nas isotermas de monocamadas iônicas insolúveis. iii-) Influência do tamanho e polaridade do \"pool\" aquoso de micelas reversas de AOT na reprotonação de sondas fotoácidas aniônicas. Em i-), foi assumido o formalismo termo-molecular para a energia livre de micelização, necessária nas estimativas da CMC e . A energia livre de micelização foi descrita como aditiva, com termos descrevendo a interação interfacial do agregado com o solvente (no caso, água), a repulsão estérica entre as \"cabeças\" do detergente, empacotamento das \"caudas\" e interação dipolar entre os \"zwitterions\". Embora nos formalismos termo-moleculares convencionais, micelas zwitteriônicas não sejam afetadas por eletrólitos, dados experimentais de supressão de fluorescência, salto de pH com sondas fotoácidas, espalhamento de luz dinâmico e estático e condutividade indicam que micelas zwitteriônicas \"ligam\" íons e \"ligam\" seletivamente. A ligação iônica pode ser tratada como um processo de absorção ou adsorção e muda a interação eletrostática das \"cabeças\". Assim, o formalismo termo-molecular foi estendido para incluir as propriedades elétricas de um capacitor com a casca externa permeável aos íons como modelo de micela zwitteriônica. Em ii-), uma nova expansão para potenciais repulsivos (chamada de expansão y) foi aplicada ao problema da interação entre detergentes iônicos em monocamadas insolúveis e comparada com a expansão virial. A interfase foi modelada como uma mistura de pseudo-fluidos bidimensionais, no nível de descrição de McMillan-Mayer (onde o solvente não aparece explicitamente, ou seja, a pressão calculada é uma pressão osmótica). A interação intermolecular na interfase foi considerada como a soma de um potencial de curto alcance (disco rígido) e um termo de longo alcance (potencial de campo médio). Na transição entre as fases líquido-condensada e líquido-expandida, a pressão do sistema é descrita por uma interpolação entre dois subsistemas na mesma densidade superficial. Finalmente em iii-), um modelo para reprotonação de uma sonda fotoácida residindo no pool aquoso de micelas reversas de AOT foi desenvolvido. A sonda (8-hidroxi-1,3,6-pirenotrisulfonato) foi tratada como uma partícula esférica posicionada no centro de um poro esférico (\"pool\" da micela reversa). A constante de reprotonação no poro foi calculada via equação de Debye-Smoluchowski junto com o potencial de força média calculado segundo a equação de Poisson-Boltzmann. O efeito da constante dielétrica aparente na reprotonação foi explorado. / The present work focus on the proposition or extension of simple models to describe the following phenomena involving amphiphile self-association aggregates: i-) Salt influence on the critical micelle concentration (CMC) and on the averaged association number () of zwitterionic micelles. ii-) Influence of the electrostatic interaction (repulsive, in this case) and of the domain size in the isotherms for ionic insoluble monolayers. iii-) Effect of size and polarity of the aqueous pool of AOT reverse micelles in the reprotonation of anionic photoacid probes. For i-), the thermo-molecular formalism for the micellization free energy, necessary for the estimate of the CMC and was assumed. The micellization free energy was described by the addition of the following terms: the interfacial interaction of the aggregate with the solvent (water, in this situation), the steric repulsion among the surfactant headgroups, the packing of the hydrocarbon tails, and the dipolar interaction among the headgroup dipoles. Although in the conventional thermo-molecular formalism zwitterionic micelles are not affected by electrolytes, experimental data including fluorescence quenching, próton jump of photoacid probes, static and dynamic light scattering, and conductivity demonstrate that these aggregates bind ions and bind selectively. The ionic binding can be treated as an absorption or adsorption process and change the electrostatic interaction among the headgroup. Thus, the thermo-molecular formalism was extended to include the electrical properties of a capacitor having the external shell permeable to ions as model of zwitterionic micelles. For ii-), a new expansion for the repulsive potentials (called y expansion) was applied to the problem of the interaction between surfactants in an insoluble monolayer and compared with the virial expression. The interface was modeled as a mixture of two-dimensional pseudo-fluids in McMillan-Mayer description level where the solvent does not appears explicitly, that is the calculated pressure is an osmotic pressure. The interfacial intermolecular interaction was considered as the sum of a short-range potential (hard disc) and a long-range term (mean field potential). In the condensed liquid and expanded liquid transition, the surface pressure can be described by an interpolation between two subsystems at the same surface density. Finally in iii-), a recombination model for a photoacid probe residing in the aqueous core of AOT reverse micelles was developed. The probe (8-hidroxi-1,3,6-pyrenetrisulfonate) treated as a spherical particle was positioned in the center of a spherical pore (micelle aqueous pool). The reprotonation was calculated by the Debye-Smoluchowski equation added to the potential of mean force derived from the Poisson-Boltzmann equation. The effect of the apparent dielectric constant in the reprotonation was explored.

La lumière que l’on reçoit du fond diffus cosmologique est décalée vers le rouge par les puits gravitationnels causés par la matière contenu dans les différentes régions de l’espace que la lumière traverse. Cet effet se nomme l’effet Sachs-Wolfe intégrée. Dans ce projet de maîtrise, nous avons calculé le terme de collision qui est dû à l’intéraction entre les photons émis par le fond diffus cosmologique et les fluctuations de densité. Ce terme vient modifier la distribution d’énergie des photons que l’on reçoit. Ce calcul est effectué en utilisant l’action de Fierz-Pauli pour trouver la section efficace de cette collision. Ce qui est nouveau dans notre démarche c’est que l’on suppose que les fluctuations de densité de l’univers entraînent un écrantage du champ gravitationnel ce qui induit une masse de Debye au graviton que l’on calcule. On utilise ensuite la théorie quantique des champs pour obtenir un terme de collision à ajouter à l’équation de Boltzmann qui dicte comment la distribution d’énergie des photons évolue. / The light we receive from the Cosmic Microwave Background is redshifted by the gravitational potential caused by the mass of the objects it meets on its way toward us. This effect is called the integrated Sachs-Wolfe effect. In this master’s thesis, we calculate a collision term between the photons and a massive scalar particle which will affect the energy distribution of the photons we observe. This calculation is made using the Fierz-Pauli action to find the cross section of this collision. What is new in our approach is that we assume that the density variation of the universe induces a shielding of the gravitational field which results in a Debye mass of the graviton. We calculate what this mass term is and we then use quantum field theory to obtain a collision term to be added to the Boltzmann equation governing how the energy distribution of photons evolves.

There is a need in the dairy industry for instrumentation capable of providing on-line information about the moisture content of cheese during manufacture. Present measurement techniques are usually performed off-line and can be susceptible to human error. It is demonstrated that microwave-based moisture sensing techniques offer a number of potential advantages over conventional methods due to the strong interaction of microwaves with water. The permittivity of cream cheese curd and low-fat cheddar cheese curd has been measured over a range of frequencies and moisture contents in order to establish the relationship between these variables. A vector reflection coefficient measurement engine based on a six-port reflectometer has been built and tested. A suitable sensing head has been fabricated from a short length of microstrip transmission line. Two sensor characterisation models have been developed and compared with measured data. A novel algorithm has been developed to resolve the ambiguity inherent in many permittivity measurement techniques. It has been discovered that surface waves can propagate on a grounded dielectric slab covered by a material with a higher dielectric constant, provided the loss factor of the covering medium is greater than zero. It has also been found that the dominant mode of microstrip can radiate when the line is covered by a high-permittivity material, although this can be suppressed if the covering material is sufficiently lossy. There are three principal conclusions to draw from the investigation in this thesis. Firstly, changes in the moisture content of cheese curd during manufacture produce measurable variations in permittivity. Secondly, these changes can be measured accurately and cheaply using off-the-shelf microwave hardware. Finally, considerable attention must be paid to the characterisation of the sensing head if the instrument is to achieve its full potential. Promising results have been obtained in this area, however certain issues pertaining to the propagation of multiple dominant modes and higher order modes have not been fully resolved and would repay further theoretical analysis.

The purpose of this study is to investigate the dielectric properties of fuel oils and their ethanol mixtures in the THz spectral region. We presented frequency dependent absorption coefficients, refractive indices, and dielectric constants calculated from the measurements of pure and mixtures of fuel oils. As the mixing ratio changes, meaningful shifts were observed in refractive index and absorption coefficient of the mixtures. For pure liquids, we used Debye model which provides a good estimate for the dielectric parameters of pure liquids in microwave region and also in the THz region. Bruggeman model, which is used for describing the interaction between liquids in binary mixtures, did not work for ethanol mixtures of gasoline within our assumptions. However, these mixtures were modeled successfully with a modified Debye model in which the mixture behavior was described with a basic contribution approach. The results suggest that there is no strong interaction between the ethanol and the molecules in the gasoline. We concluded that this new approach offers a simple and useful method to determine the concentration of ethanol in gasoline with 3% (by volume) maximum error.

The area of particle characterization is expansive; it contains many technologies and methods of analysis. Light spectroscopy techniques yield information on the joint property distribution of particles, comprising the chemical composition, size, shape, and orientation of the particles. The objective of this dissertation is to develop a hybrid scattering-absorption model incorporating Mie and Rayleigh-Debye-Gans theory to characterize submicron particles in suspension with multiwavelength spectroscopy.Rayleigh-Debye-Gans theory (RDG) was chosen as a model to relate the particles joint property distribution to the light scattering and absorption phenomena for submicron particles. A correction model to instrument parameters of relevance was implemented to Rayleigh-Debye-Gans theory for spheres. Behavior of nonspherical particles using RDG theory was compared with Mie theory (as a reference). A multiwavelength assessment of Rayleigh-Debye-Gans theory for spheres was conducted where strict adherence to the limits could not be followed. Reported corrections to the refractive indices were implemented to RDG to try and achieve Mies spectral prediction for spheres.The results of studies conducted for RDG concluded the following. The angle of acceptance plays an important role in being able to assess and interpret spectral differences. Multiwavelength transmission spectra contains qualitative information on shape and orientation of non-spherical particles, and it should be possible to extract this information from carefully measured spectra. There is disagreement between Rayleigh-Debye-Gans and Mie theory for transmission simulations with spherical scatterers of different sizes and refractive indices.

An improved crystallisation spectrometer has been designed, built and tested. It is to be used by others to gain new knowledge about the solidification of matter by study of the crystallisation of hard sphere colloid samples that are an established model for the behaviour of some aspects of atoms. In this crystallisation spectrometer, expanded and collimated green laser light is Bragg scattered from the colloidal crystals as they form, and the diffracted light is focused by a liquid filled hollow glass hemispherical lens onto low cost CCD array detectors that are rotated about the optical axis to average the intensities around the whole Debye-Scherrer cone of scattered light. The temperature of the sample is controlled to +/-0.1„a, and because of the ability to change the refractive index of the sample particles with temperature, this is utilised to control the amount of scattering from the sample Also, this spectrometer uniquely exploits the refractive index match of the colloidal particles, the solvent, the bath liquid, and the glass used for both the sample bottle and the hollow glass hemisphere. A unique facility has been incorporated to permit tumbling of the sample prior to the measurement commencing to shear-melt any pre-existing crystals. This ensures that the sample is completely fluid and is at the correct temperature at the start of the measurement. The instrument is assembled on an optical table and is computer controlled. Results presented show that this new spectrometer with its use of the whole Debye-Scherrer cone of Bragg scattered light and other enhancements gives insight into the crystallisation process more than one order of magnitude of time earlier than previous light scattering experiments, providing new knowledge about the crystallisation process.

The finite-difference time-domain (FDTD) method is one of most widely used computational electromagnetics (CEM) methods to solve the Maxwell's equations for modern engineering problems. In biomedical applications, like the microwave imaging for early disease detection and treatment, the human tissues are considered as lossy and dispersive materials. The most popular model to describe the material properties of human body is the Debye model. In order to simulate the computational domain as an open region for biomedical applications, the complex-frequency-shifted perfectly matched layers (CFS-PML) are applied to absorb the outgoing waves. The CFS-PML is highly efficient at absorbing the evanescent or very low frequency waves. This thesis investigates the stability of the CFS-PML and presents some conditions to determine the parameters for the one dimensional and two dimensional CFS-PML.The advantages of the FDTD method are the simplicity of implementation and the capability for various applications. However the Courant-Friedrichs-Lewy (CFL) condition limits the temporal size for stable FDTD computations. Due to the CFL condition, the computational efficiency of the FDTD method is constrained by the fine spatial-temporal sampling, especially in the simulations with the electrically small objects or dispersive materials. Instead of modifying the explicit time updating equations and the leapfrog integration of the conventional FDTD method, the spatial filtered FDTD method extends the CFL limit by filtering out the unstable components in the spatial frequency domain. This thesis implements filtered FDTD method with CFS-PML and one-pole Debye medium, then introduces a guidance to optimize the spatial filter for improving the computational speed with desired accuracy.

Physiological functions of a biomacromolecule seem to be closely related to its molecular conformations. The knowledge of any conformational changes due to changes in its environment may lead to a proper understanding of its functions. Hyaluronic acid, a biomacromolecule with unusually high molecular weight and some important biological functions is the subject of the present work. A temperature-dependent transition in hyaluronate solution of 120 mg/ml concentration was observed at physiological temperature. It is shown that this temperature-dependent behavior can be related to the orientational polarizability term in the Debye theory of polar molecules in liquids.

Au voisinage et au dessous des fréquences térahertz, nous avons investigué la dynamique des modes mous centraux de type Debye dans les super-réseaux ferroélectriques BaTiO3/BaxSr1-xTiO3 dans un large domaine de températures en utilisant la spectroscopie Raman polarisée. La coexistence d'un pic central et du mode mou sous-atténué suggère un caractère complexe ordre-désordre des transitions de phase successives dans ces matériaux. L'apparition du mode central prononcé pourrait expliquer l'anomalie diélectrique de type relaxateur récemment observée dans de tels super-réseaux. Nous avons exploré et comparé la dynamique des super-réseaux à trois couches et à deux couches. Nous avons montré que l'utilisation de couches de compositions chimiques différentes dans des super-réseaux multicouches permet d'obtenir des hétérostructures ayant des caractéristiques souhaitables en raison des effets de déformation entre les couches alternées et de contrôler leurs paramètres.Nous avons établi les diagrammes de phase théoriques "strain-misfit temperature" pour les couches minces de BaxSr1-xTiO3 déposées sur des substrats cubiques orientés (111). Ces diagrammes de phase sont utiles pour des applications pratiques dans l'ingénierie des couches minces. Nous avons aussi réalisé une étude expérimentale sur un film mince de Ba0.8Sr0.2TiO3 déposé sur un substrat MgO (111) pour vérifier nos prédictions théoriques. Nous avons étudié l'inversion de la polarisation induite par le champ dans la phase ferroélectrique orientée suivant l'axe C des films de structure pérovskite sous contrainte. Nous avons montré qu'en plus du mécanisme de commutation longitudinal conventionnel, lorsque le module du vecteur de polarisation orienté selon l'axe c change, les mécanismes longitudinaux-transversaux et transversaux sont aussi possibles lorsque la composante perpendiculaire de la polarisation est activée dynamiquement / We investigate near- and sub-Terahertz dynamics of soft and Debye-type central modes by the polarized Raman spectroscopy in ferroelectric BaTiO3/BaxSr1-xTiO3 superlattices in a broad temperature range. Coexistence of the central peak and the underdamped soft mode suggests complicated order-disorder character of successive phase transitions in these superlattices. The occurrence of the pronounced central mode can explain the recently observed relaxor-like dielectric anomaly in such superlattices. We explore and compare the lattice dynamics of three-layer and two-layer superlattices. We show that the using layers of different chemical compositions in multilayered superlattices one can obtain heterostructures with the desirable characteristics and realize fine tuning of their parameters due to strain effects between alternating layers.We construct the “temperature-misfit strain” theoretical phase diagrams for BaxSr1-xTiO3 thin films grown on (111)-oriented cubic substrates. The phase diagrams are useful for practical applications in thin-film engineering. We experimentally investigate a Ba0.8Sr0.2TiO3 thin film deposited on (111)MgO substrate with the aim to verify our theoretical predictions. We study the field-induced polarization reversal in the c-oriented ferroelectric phase of strained perovskite films. We show that in addition to the conventional longitudinal switching mechanism, when the c-oriented polarization vector changes its modulus, the longitudinal-transversal and transversal mechanisms when the perpendicular component of polarization is dynamically admixed are possible

Large amounts of money are being applied to the construction of the next generation of spallation sources for neutron scattering. Neutron powder diffraction instruments will be an important element of these facilities and the incorporation of detectors into these instruments with a high neutron capture efficiency is desirable. A new detector design named the Flexible Embedded Fiber Detector (FEFD) has been developed and tested for this thesis. This detector is based on wavelength shifting fibers embedded in a zinc-sulfide lithium-fluoride based scintillator. The virtue of this design is that the detecting surface can be curved around the Debye-Scherrer rings. This virtue is lacking in other detector designs, making them more complex and poorer in performance than our FEFD detectors. Monte Carlo calculations were performed to determine the neutron capture efficiencies of our FEFD detectors, which proved to be much higher than those of the proposed powder diffractometer design for the Spallation Neutron Source and about equal with the efficiency for the ISIS powder diffractometer design. Four FEFD detector prototypes were then fabricated and tested at the Intense Pulsed Neutron Source at Argonne National Laboratory. We find that our measured and calculated relative efficiencies are in good agreement.