Portland cement concrete (PCC) structures deteriorate with age and need to be maintained or replaced. Early detection of deterioration in PCC (e.g., alkali-silica reaction, freeze/thaw damage or chloride presence) can lead to significant reductions in maintenance costs. Portland cement concrete can be nondestructively evaluated by electrically characterizing its complex dielectric constant in a laboratory setting. A parallel-plate capacitor operating in the frequency range of 0.1 to 40.1 MHz was developed at Virginia Tech for this purpose. While useful in research, this approach is not practical for field implementation. In this study, a capacitor probe was designed and fabricated to determine the in-situ dielectric properties of PCC over a frequency range of 2.0 to 20.0 MHz. It is modeled after the parallel-plate capacitor in that it consists of two conducting plates with a known separation. The conducting plates are flexible, which allows them to conform to different geometric shapes. Prior to PCC testing, measurements were conducted to determine the validity of such a system by testing specimens possessing known dielectric properties (Teflon). Portland cement concrete specimens were cast (of sufficient size to prevent edge diffraction of the electromagnetic waves) having two different air contents, two void thicknesses, and two void depths (from the specimen's surface). Two specimens were cast for each parameter and their results were averaged. The dielectric properties over curing time were measured for all specimens, using the capacitor probe and the parallel-plate capacitor. The capacitor probe showed a decrease in dielectric constant with increasing curing time and/or air content. In addition to measuring dielectric properties accurately and monitoring the curing process, the capacitor probe was also found to detect the presence and relative depth of air voids, however, determining air void thickness was difficult. / Master of Science

Planar and cylindrical waveguides with linear cladding and a core with real, field dependent permittivity are considered, in particular even and odd modes are investigated.Assuming a plane wave with TE-polarization, Maxwell´s equations for the electric field lead to a nonlinear differential equation whose solution is approximated by means of a Green s function and an iteration method. Referring to a photorefractive permittivity with external field, the approximate solution is compared with the numerical solution; furthermore, the amplitude of even modes in the planar waveguide is compared with the analytically determined amplitude. In both cases, the agreement is satisfactory.The conditions of convergence of the iteration are investigated for a photorefractive permittivity with external field. It is shown that they are fulfilled for suitable choice of the width of the waveguide and the propagation constant. By means of the iteration method, the change of the linear dispersion relation due to the field dependent permittivity is described.The ratio of the power flow in the core to the total power flow is linearized in order to investigate the influence of weak nonlinearity.

Nous avons cherché dans cette thèse à caractériser la phase vitreuse formée par des molécules organiques. Pour cela, nous y avons dilué des molécules sur lesquelles on a greffé un fragment d’azobenzène, de façon à pouvoir les orienter sélectivement en les illuminant. On souhaite ainsi s’approcher de la procédure de clouage aléatoire, qui permet en théorie et par simulations de caractériser d’une manière nouvelle la phase vitreuse "idéale", stable thermodynamiquement, qui se formerait pendant la transition vitreuse. On caractérise en temps réel les effets de l’illumination sur ces molécules modifiées (isomérisations cis-trans, orientation) par spectroscopie d’absorption UV polarisée. On mesure l’impact de l’illumination sur la transition vitreuse de leur matrice par spectroscopie diélectrique. Nous avons observé une accélération de la dynamique pendant illumination (diminution du temps de relaxation alpha). Celle-ci n’est pas due à l’orientation de l’azobenzène mais aux autres effets de l’illumination : les isomérisations cycliques cis-trans, et la présence d’isomères cis. Au total, la viscosité du verre est divisée par presque 50 en dessous de Tg, ce qui représente une augmentation de la température effective de l’échantillon de plus de 6K, alors que le chauffage réel dû à l’illumination est inférieur à 100mK. Derrière ces deux effets majoritaires, nous avons repéré que plus l’orientation est grande, plus le temps de relaxation alpha est grand, toute chose égale par ailleurs. Cette influence de l’orientation semble être très forte car nos fractions orientées sont faibles. En suivant les prédictions de la théorie RFOT, on trouve que la transition vitreuse idéale aurait lieu pour une concentration en molécules orientées entre 0,5 et 2% à Tg. Les expériences de random pinning sur des verres moléculaires semblent donc bien réalisables avec l’azobenzène. On jette dans cette thèse les bases d’une nouvelle voie expérimentale qui nous semble prometteuse pour l’étude de la transition vitreuse. / In this thesis we have sought to characterize the glassy phase formed by organic molecules. To do this, we diluted molecules on which we grafted an azobenzene fragment, so that we could selectively orient them by illuminating them. In this way, we wish to approach the random pinning procedure, which makes it possible in theory and by simulations to characterize in a new way the "ideal" thermodynamically stable glass phase that would be formed during the glass transition. The effects of illumination on these modified molecules (cis-trans isomerizations,orientation) are characterized in real time by polarized UV absorption spectroscopy. The impact of illumination on the glass transition of the matrix is measured by dielectric spectroscopy. We observed an acceleration of the dynamics during illumination (decrease of the alpha relaxation time). This is not due to the orientation of azobenzene but to other effects of illumination : cyclic cis-trans isomerizations, and the presence of cis isomers. In total, the viscosity of the glass is divided by almost 50 below Tg, which represents an increase in the effective temperature of the sample of more than 6K, while the actual heating due to illumination is less than 100 mK. Behind these two majority effects, we have identified that the greater the orientation, the greater the alpha relaxation time, all other things being equal. This influence of orientation seems to be very strong because our oriented fractions are small. Following the predictions of the RFOT theory, we find that the ideal glass transition would occur for a concentration of oriented molecules between 0.5 and 2% at Tg. Therefore random pinning experiments on molecular glasses seem to be feasible using azobenzene. In this thesis, we are laying the foundations for a new experimental approach that seems promising to us for the study of glass transition.

This dissertation work concentrates on novel reconfiguration technologies, including design, microfabrication, and characterization aspects with an emphasis on their applications to multifunctional recon-figurable antennas. In the literature, reconfigurable antennas have made use of various reconfiguration techniques. The most common techniques utilized revolved around switching mechanisms. Other techniques such as the incorporation of variable capacitors, varactors, and physical structure manipulation surfaced recently to overcome many problems faced in using switches and their biasing. Usage of fluids (micro-fluidic or otherwise) in antennas provides a conceptually easy reconfiguration mechanism in the aspect of physical alteration. However, a requirement of pumps, valves, etc. for liquid transportation makes the antenna implementations rather impractical for the real-life scenarios. This work reports on design and experiments conducted to evaluate the electrowetting on dielectric (EWOD) driven digital microfluidics as a reconguration mechanism for antennas.

L'interaction entre impulsions lasers ultra-brèves et matériaux diélectriques est un sujet d'étude en constant renouvellement, motivé aussi bien par la naissance d'une multitude d'applications (micro-usinage laser, opérations de la cornée, ...) que par ses aspects fondamentaux (génération d'harmoniques d'ordre élevé, électronique au cycle optique, ...). Pourtant, les mécanismes sous-jacents à cette interaction sont encore mal compris, en particulier d'un point de vue quantitatif. En effet, une bonne partie des phénomènes ont lieu durant le passage de l'impulsion laser, c'est-à-dire pendant quelques dizaines de femtosecondes. De surcroît, les éclairements impliqués dans l'interaction sont élevés : quelques dizaines de TW/cm^2. La compréhension et la quantification des processus élémentaires ayant lieu durant l'interaction requiert donc de concevoir des expériences sur mesure ainsi que d'effectuer un travail approfondi de modélisation. Dans ce manuscrit sont présentées deux techniques expérimentales complémentaires utilisées durant la thèse : l'interférométrie fréquentielle et la spectroscopie d'absorption résolues en temps. Ces deux techniques sont employées pour étudier les processus électroniques d'excitation et de relaxation dans trois matériaux distincts : le quartz, le saphir et l'oxyde de magnésium. La quasi-intégralité des résultats expérimentaux sont analysés à l'aide d'un modèle en équation de taux multiples (MRE) permettant de discriminer l'importance relative de chacun des processus pris en compte. Tout d'abord, une preuve expérimentale directe de l'existence de l'ionisation par impact dans le quartz est présentée. Ces résultats ont été obtenus par l'exposition de l'échantillon à une série de deux impulsions, ce qui permet de moduler indépendamment la densité et la température du plasma. Les résultats expérimentaux sont reproduits avec succès par le modèle MRE intégrant l'ionisation multiphotonique, le chauffage des porteurs photo-excités ainsi que l'ionisation par impact comme processus d'excitation. Nous nous concentrons ensuite sur une seconde série de résultats concernant la relaxation du saphir après excitation induite par laser. Un nouveau mécanisme de relaxation est proposé et testé par la modélisation pour tenter d'expliquer la dynamique de ce processus. Ce mécanisme implique la formation d'excitons auto-piégés puis leur recombinaison. Enfin, le modèle MRE est appliqué à la détection de seuils d'ablation dans les trois solides. Le choix du critère physique déterminant ce seuil, sujet soumis à d'intenses débats dans la littérature, est alors discuté. / The interaction between an ultrashort laser pulse et dielectric materials is a constantly evolving field motivated by the birth of various applications (laser micro-machining, cornea surgery, ...) as well as its fundamental aspects (high-order harmonic generation, electronics at optical-cycle regime, ...). However, the underlying mechanisms of this interaction are still to be understood, especially from a quantitative point of view. Indeed, most phenomena occur during the pulse propagation through the material (i.e. in a few tens of femtoseconds). Moreover, the involved intensities are very high: a few tens of TW/cm^2. These two aspects make it difficult to study this interaction. To push the understanding forward, it is necessary to design new experiments and carry out an extensive work in modelling. Two complementary experimental techniques are presented in this manuscript: time resolved spectral interferometry and absorption spectroscopy. These two techniques are used to study elementary excitation and relaxation electronic processes in three different materials: Quartz, sapphire and magnesium oxide. Almost all experimental results are analyzed using a multiple rate equations (MRE) model allowing us to discriminate the relative importance of each of these processes. Firstly, a direct experimental proof of the existence of impact ionization in quartz is presented. These results have been obtained by exposing the sample to a sequence of two laser pulses, allowing us to tune independently both density and temperature of the plasma. The experimental results are successfully reproduced by the MRE model including multiphoton ionization, inverse bremsstrahlung and impact ionization as excitation processes. We then focus on another series of results on sapphire relaxation after laser-induced excitation. A new relaxation mechanism is proposed and tested by modelling to attempt to explain the dynamic of this process. This mechanism involves the formation of self-trapped excitons and their recombination. Finally, the MRE model is applied to the detection of the laser-induced ablation threshold in all three solids. The choice of the physical criterion defining this threshold, a subject that has caused intense debates over the past years, is discussed.

abstract: This study aims to address the deficiencies of the Marcus model of electron transfer (ET) and then provide modifications to the model. A confirmation of the inverted energy gap law, which is the cleanest verification so far, is presented for donor-acceptor complexes. In addition to the macroscopic properties of the solvent, the physical properties of the solvent are incorporated in the model via the microscopic solvation model. For the molecules studied in this dissertation, the rate constant first increases with cooling, in contrast to the prediction of the Arrhenius law, and then decreases at lower temperatures. Additionally, the polarizability of solute, which was not considered in the original Marcus theory, is included by the Q-model of ET. Through accounting for the polarizability of the reactants, the Q-model offers an important design principle for achieving high performance solar energy conversion materials. By means of the analytical Q-model of ET, it is shown that including molecular polarizability of C60 affects the reorganization energy and the activation barrier of ET reaction. The theory and Electrochemistry of Ferredoxin and Cytochrome c are also investigated. By providing a new formulation for reaction reorganization energy, a long-standing disconnect between the results of atomistic simulations and cyclic voltametery experiments is resolved. The significant role of polarizability of enzymes in reducing the activation energy of ET is discussed. The binding/unbinding of waters to the active site of Ferredoxin leads to non-Gaussian statistics of energy gap and result in a smaller activation energy of ET. Furthermore, the dielectric constant of water at the interface of neutral and charged C60 is studied. The dielectric constant is found to be in the range of 10 to 22 which is remarkably smaller compared to bulk water( 80). Moreover, the interfacial structural crossover and hydration thermodynamic of charged C60 in water is studied. Increasing the charge of the C60 molecule result in a dramatic structural transition in the hydration shell, which lead to increase in the population of dangling O-H bonds at the interface. / Dissertation/Thesis / Doctoral Dissertation Chemistry 2019

The use of electromagnetic waves as a nondestructive evaluation technique to evaluate Portland cement concrete (PCC) structures is based on the principle that a change in the structure, composition, or properties of PCC results in a change in its dielectric properties. The coaxial transmission line is one of the few devices that can measure the dielectric properties of PCC at a frequency range of 100-1000 MHz. A coaxial transmission line developed at Virginia Tech was used to study the effect of moisture, type of aggregate, water/cement ratio, curing period, admixture type (microsilica, superplasticizer, and shrinkage admixture), and chloride content on the dielectric properties of PCC. Measurements were conducted in the time domain and converted to the frequency domain using Fast Fourier Transform. The research found that an increase in the moisture content of PCC resulted in an increase in the dielectric constant. Mixes containing limestone aggregate had a greater dielectric constant than those containing granite. The dielectric constant decreased with curing period due to the reduction in free water availability. Mixes containing higher water/cement ratios exhibited a higher dielectric constant, especially in the initial curing period. The admixtures did not significantly affect the dielectric constant after one day of curing. After 28 days of curing, however, all three admixtures had an effect on the measured dielectric constant as compared to control mixes. Chloride content had a significant effect on the loss part of the dielectric constant especially during early curing. A relationship was also established between the chloride permeability (based on conductance measurements) of PCC and its dielectric constant after 75 days of moist curing. / Master of Science

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