Dielectric permittivity measurements provide important input to engineering and scientific disciplines due to the effects of permittivity on the interactions between electromagnetic energy and materials. A novel ring resonator design is presented for the measurement of permittivity of low dielectric constant foams. A review of dielectric material properties and currently available measurement methods is included. Measurements of expanded polystyrene are reported and compared with results from the literature; good agreement between measurements and published results is shown.

Cemented Paste Backfill (CPB) is a relatively new backfilling technology for which a better understanding of binder hydration is required. This research uses electromagnetic (EM) wave-based techniques to non-destructively study a CPB consisting of tailings, sand, process water and binder (90% blast-furnace slag; 10% Portland cement). EM experiments were performed using a broadband network analyzer (20 MHz to 1.3 GHz) in the lab and capacitance probes (70 MHz) in the lab and field. Results showed that the EM properties are sensitive to curing time, operating frequency and specimen composition including binder content. The volumetric water content interpreted from dielectric permittivity varied little with curing. Temporal variations in electrical conductivity reflected the different stages of hydration. Laboratory results aided interpretation of field data and showed that a reduction in binder content from 4.5% to 2.2% delays setting of CPB from 0.5 days to over 2 days, which has important implications for mine design.

Cemented Paste Backfill (CPB) is a relatively new backfilling technology for which a better understanding of binder hydration is required. This research uses electromagnetic (EM) wave-based techniques to non-destructively study a CPB consisting of tailings, sand, process water and binder (90% blast-furnace slag; 10% Portland cement). EM experiments were performed using a broadband network analyzer (20 MHz to 1.3 GHz) in the lab and capacitance probes (70 MHz) in the lab and field. Results showed that the EM properties are sensitive to curing time, operating frequency and specimen composition including binder content. The volumetric water content interpreted from dielectric permittivity varied little with curing. Temporal variations in electrical conductivity reflected the different stages of hydration. Laboratory results aided interpretation of field data and showed that a reduction in binder content from 4.5% to 2.2% delays setting of CPB from 0.5 days to over 2 days, which has important implications for mine design.

The key features of dynamics of ultraslowing glass forming systems are their universality in diversity. Its origin is recognized as one of the greatest challenges of condensed matter physics and materials engineering in the XXI century. Similar phenomena are observed on approaching the glass transition in low molecular weight supercooled liquids, polymers, colloidal fluids as well as in solids, for instance in orientationally disordered crystals, spin glass-like magnetic, vortex glasses. Pre-vitreous dynamics is also proposed as a general reference for the category of complex liquids/soft matter systems. The upsurge of the primary relaxation time or related dynamical properties is the basic physical phenomena of the still mysterious previtreous behavior. This means a much more pronounced slowing down than the Arrhenius pattern observed far above the glass transition temperature. Portraying this behavior constitutes one of key checkpoints for theoretical models developed to unwind the glass transition puzzle. However, none of the aforementioned features can answer the understanding that governs the increase of relaxation time in liquids upon cooling. In this thesis we focus on the above questions studying the dynamics of some materials for which their molecules can retain a translational order being orientationally disordered between them upon cooling, which are referred to plastic phases or orientationally disordered (OD) crystalline phases. The work presented in this thesis potentially extends the knowledge of dynamics of OD phases and orientationally glasses (OG), a research topic which has gained interest during the last decades. Through this study, especial attention has been devoted to the phenomenological equations accounting to the temperature dependence of the mean relaxation time describing the orientational dynamics .The study was carried out by the use of BDS as well as two complementary experimental techniques. We show distortion-sensitive and derivative-based empirical analysis of the validity of leading equations for portraying the previtreous evolution of primary relaxation time. A new method for studying the dynamics of glass forming systems is introduced and the minimization procedure is validated and discussed. We present the results divided in two topics, the dynamics of the pure compounds and mixed crystals and the derivative analysis through different existing models. In the first topic we focus on the dynamics of the pure compounds and mixed crystals formed between cycloheptanol and cyclooctanol as well as the a-relaxation dynamics of 1-cyano-adamantane and its mixtures with 1-chloro-adamantane. The second topic is divided in two groups of models, linearized and non-linearized models. In the linearized models we show the application of the derivative based, distortion-sensitive analysis to liquid crystals (LC) and OD phases. We also discuss the results concerning to the cases of the olygomeric liquid epoxy resin (EPON828), neopentylalcohol and neopentylglycol mixture, isooctylcyanobiphenyl and propylene carbonate. The possible empirical correlations between one of the linearized models with the universal pattern for the high frequency wing of the loss curve for primary relaxation time for LCs and OD phases is also shown. In the final part we show that the form of the equation recently introduced by Mauro et al. does not allow a similar straightforward linearization procedure. Unlike the previous models, the involved parameters are not correlated with the slope and the intercept of a linear function. In order to solve this problem, we have introduced the concept of the enthalpy space. The evidences of the existence of crossovers as well as quantitative descriptions are discussed. We show also a new procedure for detecting the crossover in a very easy way. A new kind of crossovers which seems to be impossible to be detected by the classical Stickel transformation is presented. / La principal característica de la dinámica de sistemas vítreos viscosos, es su universalidad en la diversidad. Su origen es uno de los mayores desafíos de la física de la materia condensada y de la ingeniería de materiales en el siglo XXI. La fenomenología típica de las fases vítreas se observan cerca de la transición vítrea en líquidos subenfriados de bajo peso molecular, polímeros, fluidos coloidales, así como en los sólidos con fases orientacionalmente desordenadas. La imposibilidad de explicar las causas del gran aumento del tiempo de relajación al enfriar un líquido, constituye uno de los problemas más importantes no resueltos en materia condensada. Con el objetivo de dar respuesta a dicha interrogante, se han propuesto modelos termodinámicos y dinámicos que han resultado inconsistentes. En esta tesis nos centramos en dicha problemática, estudiando la dinámica orientacional de algunos materiales que al ser enfriados pueden conservar un orden traslacional mientras que se conserva el desorden orientacional de las moléculas que los forman. Dichas fases se conocen como fases plásticas u orientacionalmente desordenadas (OD). El trabajo presentado en esta tesis amplía el conocimiento de la dinámica de dichas fases, un tema de investigación cuyo interés ha aumentado durante las últimas décadas. Se ha dedicado una atención especial a las ecuaciones fenomenológicas que describen la dependencia del tiempo de relajación con la temperatura. El estudio se ha llevado a cabo mediante el uso de espectroscopía dieléctrica de banda ancha, así como mediante el uso de técnicas experimentales complementarias. Se ha introducido un nuevo método para el estudio de la dinámica de los sistemas que dan lugar a fases vítreas. El método ha sido validado y discutido. Los resultados de esta tesis se presentan divididos en dos temas, por un lado, la dinámica de compuestos puros y de los cristales mixtos y, por otro, el análisis mediante el método derivativo aplicado a los diferentes modelos físicos existentes. En el primer tema nos centramos en la dinámica de los compuestos puros y los cristales mixtos formados por cicloheptanol y ciclooctanol, así como la dinámica de la relajación alfa en 1-ciano-adamantano y sus mezclas con 1-cloro-adamantano. El segundo tema se divide en dos grupos de modelos, los modelos lineales y no lineales. En los modelos lineales se muestra la aplicación del procedimiento de derivativo en los cristales líquidos (CL) y las fases OD. También se discuten los resultados relativos a los casos de la resina líquida (EPON828), la mezcla neopentil-alcohol y neopentil-glicol, el carbonato de propileno, así como el CL isooctilcianobifenil. Se discute también la existencia de posibles correlaciones empíricas entre uno de los modelos lineales con el patrón universal para la parte de alta frecuencia de la curva de pérdidas dieléctricas de la relajación primaria para las fases CL y OD. En la parte final se muestra que la forma de la ecuación introducida recientemente por Mauro et al. no permite la linearización mediante el método derivativo. A diferencia de los modelos anteriores, los diferentes parámetros no están correlacionados con la pendiente y el origen de coordenadas de una función lineal. Para resolver este problema, hemos introducido el concepto del espacio entálpico. Se analiza también la existencia de cambios de comportamiento dinámicos y se aportan descripciones cuantitativas. Se muestra también un nuevo procedimiento para detectar los cambios dinámicos de una manera fácil, que permite incluso detectar aquéllos que son obviados mediante el método clásico de Stickel.

A controlled column experiment was conducted to investigate the geophysical response of gasoline spills into the partially saturated sand column. The column was 0.61 diameter (ID) and 2 m high cylindrical polyvinyl chloride, which was packed with the Borden sand to a height of 1.95 m, flushed with CO2, saturated, and drained to a height of 0.73 m. The monitoring techniques used for this experiment was DC resistivity and time domain reflectometry (TDR) methods. The column was equipped with resistivity electrodes and TDR probes, which were placed on the column wall vertically with 3 cm intervals, on opposite sides, two monitoring wells, an injection well, a manometer, an outlet/inlet system, and a vent. A total amount of 5 liters of standard API 91-01 gasoline was added to the system in steps of 1, 2, and 2 liters to examine the geophysical response to different amounts of gasoline. Measurements were taken before and after each injection and also during subsequent fluctuation of the water table. Both monitoring techniques were able to record even the minor changes in the trend of conductivity and permittivity profiles due to the addition of the small amount of gasoline during the first spill. The conductivity and permittivity profiles obtained before lowering the water level below the original level and those obtained after the water level reached to the original level do not match, which is an indication of entrapped gasoline inside the pores. Two core samples was taken from the sand symmetrically after each water table fluctuation and analyzed for total petroleum hydrocarbon (TPH) analysis and the results were compared to the conductivity and permittivity results. The conductivity profile obtained using DC resistivity method was compared to that of obtained using TDR method. The profiles match in the saturated zone where all of the pores are connected with water and therefore electrolytic conduction is predominant. In the unsaturated zone, where there is low pore water connectivity, TDR measured conductivity values are higher than those measured using the resistivity method. Water saturation values were calculated using conductivity and permittivity values before and after each injection. Different values of saturation exponent (n) were tested for Archie’s law until an appropriate value was found which gave the best water saturation from conductivity data for clean Borden sand. Then, the water saturation obtained from permittivity values using Topp’s equations for different materials were compared to that of obtained from conductivity values using Archie’s equation. Topp’s equation for 30 µm glass beads provided the best match. Furthermore, other equations developed by other researchers were examined to obtain water saturation profiles from the permittivity values; all of them overestimate the water saturation for Borden sand. The water saturation profiles after the gasoline spills obtained using both Archie’s law and Topp’s equation do not match, perhaps because both equations were developed for three-phase (water-solid-air) systems.

A controlled column experiment was conducted to investigate the geophysical response of gasoline spills into the partially saturated sand column. The column was 0.61 diameter (ID) and 2 m high cylindrical polyvinyl chloride, which was packed with the Borden sand to a height of 1.95 m, flushed with CO2, saturated, and drained to a height of 0.73 m. The monitoring techniques used for this experiment was DC resistivity and time domain reflectometry (TDR) methods. The column was equipped with resistivity electrodes and TDR probes, which were placed on the column wall vertically with 3 cm intervals, on opposite sides, two monitoring wells, an injection well, a manometer, an outlet/inlet system, and a vent. A total amount of 5 liters of standard API 91-01 gasoline was added to the system in steps of 1, 2, and 2 liters to examine the geophysical response to different amounts of gasoline. Measurements were taken before and after each injection and also during subsequent fluctuation of the water table. Both monitoring techniques were able to record even the minor changes in the trend of conductivity and permittivity profiles due to the addition of the small amount of gasoline during the first spill. The conductivity and permittivity profiles obtained before lowering the water level below the original level and those obtained after the water level reached to the original level do not match, which is an indication of entrapped gasoline inside the pores. Two core samples was taken from the sand symmetrically after each water table fluctuation and analyzed for total petroleum hydrocarbon (TPH) analysis and the results were compared to the conductivity and permittivity results. The conductivity profile obtained using DC resistivity method was compared to that of obtained using TDR method. The profiles match in the saturated zone where all of the pores are connected with water and therefore electrolytic conduction is predominant. In the unsaturated zone, where there is low pore water connectivity, TDR measured conductivity values are higher than those measured using the resistivity method. Water saturation values were calculated using conductivity and permittivity values before and after each injection. Different values of saturation exponent (n) were tested for Archie’s law until an appropriate value was found which gave the best water saturation from conductivity data for clean Borden sand. Then, the water saturation obtained from permittivity values using Topp’s equations for different materials were compared to that of obtained from conductivity values using Archie’s equation. Topp’s equation for 30 µm glass beads provided the best match. Furthermore, other equations developed by other researchers were examined to obtain water saturation profiles from the permittivity values; all of them overestimate the water saturation for Borden sand. The water saturation profiles after the gasoline spills obtained using both Archie’s law and Topp’s equation do not match, perhaps because both equations were developed for three-phase (water-solid-air) systems.

The composition-dependent Curie temperature and bias-dependant dielectric permittivity of Barium Strontium Titanate (BST) makes it very attractive for tunable application in the RF/Microwave regime. In this research work, the performance of BST varactors fabricated on the conventional Pt/Ti/SiO2/Si bottom electrode stack were compared with those fabricated using chemical vapor deposited Nanocrystalline Diamond (NCD) as the diffusion barrier layer instead of SiO2. The varactors fabricated on NCD films displayed much better symmetry in capacitance-voltage behavior and better overall quality factors than varactors fabricated on SiO2. The improvement in performance can be attributed to existence of stable interfaces in the devices fabricated on NCD which reduced the bottom electrode losses at high frequencies. The SiO2 based BST varactors on the other hand displayed better reliability and breakdown fields. The main purpose of this research work is to develop a robust Metal Insulator Metal (MIM) structure to achieve better all round performance of BST varactors. In the second part of this research work, the prospect of developing diamond based layered Surface Acoustic Wave (SAW) devices using Ba0.8Sr0.2TiO3 as the piezoelectric layer is investigated. Structural characterization of BST thin films deposited on Si/NCD/Pt and Si/SiO2/Ti/Pt stack were performed using X-Ray Diffraction (XRD) and Atomic Force Microscopy (AFM). Cross-sectional studies on the two stacks were performed using Scanning Electron Microscopy (SEM). X-Ray Mapping (XRM) was then done to ascertain the quality of the interfaces and to check for interdiffusion between layers. MIM structures in the Coplanar Waveguide (CPW) configuration were fabricated using conventional lithography and etching techniques for high frequency measurements. The performance of the fabricated varactors was characterized from 100 MHz to 1 GHz. For the SAW application, structural characterization of Ba0.8Sr0.2TiO3 on Chemical Vapor Deposited (CVD) diamond was done and the deposition procedure was optimized to obtain thick BST films. SAW bandpass filters and resonators were designed wherein the device geometry was varied over a wide range in order to characterize the variation in device performance with geometry. Finally interdigital capacitor structures were fabricated and used for conducting Curie temperature measurements on the deposited BST films in order to determine the operation range of the deposited BST films.

La quantité et la distribution de l'eau interstitielle dans l'espace poral des milieux cimentaires sont des marqueurs fondamentaux de la durabilité des structures de Génie Civil en béton. La connaissance de ces grandeurs est également importante pour l'interprétation de certains essais non destructifs mis en œuvre pour évaluer les performances mécaniques des ouvrages ou détecter certains défauts. L'évaluation de la teneur en eau par méthode non-destructive requiert l'utilisation d'une grandeur intermédiaire telle que la permittivité diélectrique. La relation entre cette propriété électromagnétique et la teneur en eau dépend alors de la composition et donc de la formulation du béton. En électromagnétisme, les lois d'homogénéisation permettent de lier la permittivité effective d'un matériau hétérogène avec la permittivité intrinsèque et la fraction volumique de chaque hétérogénéité présente. Afin de pallier le temps important requis pour l'établissement d'une courbe de calibration expérimentale propre à chaque formulation, l'étude présentée propose la mise en place d'une démarche d'homogénéisation de la permittivité pour lier quantité d'eau présente dans un béton et permittivité macroscopique du matériau. Les travaux présentés rapportent la fabrication, la modélisation et l'utilisation de sondes coaxiales ouvertes pour la mesure de la permittivité complexe de matériaux solides et liquides. Le concept d'estimation de la teneur en eau par utilisation de lois d'homogénéisation est validé pour le cas d'un sable partiellement saturé en eau. Au vu des résultats prometteurs obtenus par modélisation analytique, des schémas d'homogénéisation sont combinés lors d'un processus de remontée d'échelle depuis celle des hydrates jusqu'à celle des granulats, en tenant compte de la morphologie de la microstructure. Les propriétés intrinsèques des principaux constituants d'un béton (granulats, hydrates, ciment anhydre) sont alors mesurées par sonde coaxiale et utilisées en données d'entrée du modèle construit. Une bonne cohérence est observée entre parties réelles de la permittivité simulées et mesurées, pour des échantillons de pâtes de ciment, mortiers et bétons. A la différence des lois expérimentales et empiriques, le modèle construit se caractérise par un temps de calcul quasi-instantané et peut être adapté d'une formulation de béton à une autre en fonction du type de ciment utilisé, de la nature et de la quantité de granulats ou encore de la porosité accessible à l'eau du matériau. / Prediction of delayed behavior in concrete can be significantly improved by monitoring the amount and spatial distribution of water within a concrete structure over time. Water content of cement-based materials can also be required to interpret non-destructive tests such as ultrasonic and radar measurements. Electromagnetic properties of heterogeneous and porous materials, such as dielectric permittivity, are closely related to water content. Measurement of these properties is thus a common non-destructive technique used to assess the moisture content, but a calibration curve is required to link the measured permittivity to the saturation degree. This curve can be determined experimentally, or from empirical models. However, the first approach is tedious and time consuming, while the second one is not adapted to concrete. Hence, this contribution proposes an alternative route, relying on electromagnetic homogenization schemes, to connect the macroscopic permittivity of cement-based materials with the water content of the structure. Therefore, different open-ended coaxial probes were designed, modelled and tested in order to perform complex permittivity measurements of both solids and liquids. The homogenization approach is first validated on unsaturated sand. Then, the permittivity of concrete components (aggregates, hydrates, interstitial liquid, anhydrous cement) was assessed by means of coaxial probe measurements. Finally, a specific combination of analytical homogenization laws taking into account the microstructure's morphology of the material is built. Results show that there is a good correlation between the model and measurements acquired on different cement pastes, mortars and concretes, at different saturation degrees. The model is characterized by a quasi-instantaneous calculation time and can be adapted to different concretes depending on cement type, nature and quantity aggregates or porosity.

No description available.

In this work the electrical insulating properties of the nanocomposite materials based on poly(ethylene-co-butyl acrylate) filled with alumina nanoparticles are studied. The dielectric properties chosen for the evaluation are the dielectric permittivity and loss as well as the breakdown strength and the pre-breakdown currents. The reason for choosing these particular properties is partly due to the importance of these for the general electrical applications and partly due to the uncertainties involved for these particular properties of the nanocomposite materials. The importance of moisture absorption for the dielectric properties is outlined in this work. All measurements were performed in both dry conditions and after conditioning of the materials in humid environment until saturation. The data for moisture absorption was taken from the water absorption study performed at the Department of Fibre and Polymer Technology, KTH. The dielectric spectroscopy in frequency domain was employed for measuring dielectric permittivity and loss. Havriliak-Negami approximation was used for characterization of the measurement data and at the same time ensuring the fulfillment of the Kramers-Kronig relations. Results from the dielectric spectroscopy study in dry conditions suggest that dielectric spectroscopy can be used for evaluating nanoparticle dispersion in the host matrix, based on correlation between the morphology data obtained from SEM investigation and the scatter in the dielectric loss. The dielectric spectroscopy study performed on the nanocomposites after conditioning in humid environment showed that absorbed moisture has a distinct impact on the dielectric loss. Especially pronounced is its’ influence on the frequency behavior, when the dielectric loss peaks are shifted towards higher frequencies with increased moisture content. The nanocomposite materials characterized by higher specific surface area generally exhibit higher dielectric losses. Surface functionalization of the nanoparticles does not seem to have much influence on the dielectric loss in dry conditions. After conditioning in humid environment, however, the surface modification was shown to have a significant impact. Temperature is another significant factor for the frequency behavior of the dielectric loss: it was found that the studied nanocomposites can be characterized by Arrhenius activation. The breakdown strength and pre-breakdown currents study outlined the influence of moisture as well. The study indicated that surface treatment of the nanoparticles can enhance properties of the nanocomposite materials, namely aminopropyltriethoxy silane was an especially successful choice: • The highest breakdown strength was determined by the study for NDA6 material formulation in dry conditions. • After conditioning in humid environment the NDA6 material continued showing the best breakdown strength among the nanocomposite mate rials, as well as this value was close to the breakdown strength of the reference unfilled material. This study confirms the existence of the optimal nanofiller content or rather optimal specific surface area of the dispersed nanoparticles in the host matrix. The latter is supported by the comparison between the nanocomposites based on nanoparticles with two different specific surface areas, which shows that the dielectric properties worsen, i.e. the dielectric losses increase and the influence of absorbed moisture on the breakdown strength becomes more pronounced, for nanomaterials with larger specific surface area. The pre-breakdown currents were found to follow space-charge limited conduction mechanism reasonably well. The following conduction regimes were identified: constant region (likely due to measurement difficulties at low field strengths), Ohm’s regime, trap-filled-limit regime and trapfree dielectric regime. The breakdown usually occurred either during the trap-filled-limit regime, when the current increased dramatically for the small change in electric field, or during the trapfree dielectric regime. The threshold values between different conduction regimes seem to correlate well with the oxidation induction times (OIT), which in turn depend on the total specific surface area. The pre-breakdown currents tend to be highest for the materials filled with the untreated nanoparticles. Increased absorbed moisture content causes higher pre-breakdown currents for the nanocomposite materials, while for the reference unfilled material the pre-breakdown currents do not show such tendency. Generally it can be said that the repeatability in the measured data is higher for the nanocomposite materials in comparison to the unfilled host material, as was demonstrated by both dielectric spectroscopy and breakdown studies. / <p>QC 20130207</p>