A caracterização dielétrica de um material pode ser usada como uma técnica não destrutiva para avaliar e monitorar sua qualidade, bem como no entendimento da relação estrutura-propriedade de um material, através de suas propriedades dielétricas em função da frequência, temperatura, composição química do material, dentre outros. Na literatura há escassez de trabalhos e dados de caracterização dielétrica de filmes a base de biopolímeros. Diante desse contexto, o objetivo deste trabalho foi o desenvolvimento e a construção de uma instrumentação alternativa a equipamentos disponíveis no mercado, como analisadores de rede e de impedância, que pudesse ser utilizada para a caracterização dielétrica de filmes biodegradáveis a base de gelatina. Foi utilizado o método de placas paralelas na determinação da parte real da permissividade conhecida como permissividade relativa ou constante dielétrica (ε\'). O circuito utilizado para a instrumentação foi um oscilador astável com funcionamento baseado no amplificador operacional (741) chaveado pela carga de um capacitor de placas paralelas cujo dielétrico foi uma amostra de filme biodegradável. A partir dos valores da frequência de oscilação e geometria do capacitor, foi possível calcular a capacitância de cada amostra e, consequentemente obter os valores da permissividade relativa do filme, usando relações básicas bem estabelecidas. Os filmes de gelatina foram produzidos pela técnica de casting sendo utilizados como plastificantes o glicerol (G), o sorbitol (S) e suas misturas, na proporção (G:S) de 30:70, 50:50 e 70:30. Os filmes foram caracterizados quanto à umidade e cristalinidade. A permissividade relativa (ε\') dos filmes, determinada a temperatura ambiente, foi avaliada em função da frequência (5 a 50 kHz), tempo de armazenamento, do teor de umidade e tipo de plastificante. A instrumentação projetada e construída foi capaz de medir com precisão a permissividade relativa das amostras, sendo que essa propriedade diminuiu com o aumento da frequência para todos os filmes. Mantendo-se a frequência constante, não houve variação de ε\' para os filmes de gelatina, independente do plastificante, ao longo de um mês de armazenamento a 24 ± 3 °C. O efeito da umidade foi observado em frequências menores que 25 kHz, sendo que quanto maior o teor de umidade maior a permissividade relativa. O efeito do tipo de plastificante na permissividade relativa dos filmes foi observado a baixas frequências (5 kHz) e filmes plastificados com sorbitol apresentaram maiores valores de ε\'. Os filmes plastificados com maior teor de umidade apresentaram menor cristalinidade, portanto maior mobilidade molecular e consequentemente maior a permissividade relativa. / The dielectric characteristics of a material can be used as a non-destructive technique to evaluate and monitor the quality as well as the understanding of the structure-property of a material, through its dielectric properties as a function of frequency, temperature, chemical composition of the material, among others. In the literature there are few studies and data of dielectric characterization of films based on biopolymers. In this context, the objective of this research was the development and construction of an alternative instrumentation equipment on the market, such as network and impedance analyzers, which could be used for the dielectric characterization of biodegradable films based on gelatin. The method of parallel plates was used to determine the real part of permittivity known as relative permittivity or dielectric constant (ε\'). The circuit used for the instrumentation was an astable oscillator operation based on operational amplifier (741) switched by the load of a parallel plate capacitor whose dielectric was a sample of the biodegradable film. From the values of the oscillation frequency and geometry of the capacitor, it was possible to calculate the capacitance of each sample and thus obtaining values of the relative permittivity of the film, using well established basic relationships. Gelatin films were produced by casting technique being used as plasticizer glycerol (G), sorbitol (S) and mixtures thereof, in proportion (G:S) 30:70, 50:50 and 70:30. The films were characterized for moisture and crystallinity. The relative permittivity (ε\') of the films, determined at room temperature, was evaluated as a function of frequency (5-50 kHz), storage time, moisture content and type of plasticizer. The designed and constructed instrumentation was able to accurately measure the relative permittivity of the samples, being that this property decreased with increasing frequency for all films. Keeping constant frequency, there was no variation in ε\' for the gelatin films, independent of the plasticizer over one month of storage at 24 ± 3 °C. The moisture effect was observed at frequencies lower than 25 kHz, how bigger the moisture content the higher the relative permittivity. The effect of the plasticizer type in relative permittivity of the films were observed at low frequency (5 kHz) and plasticized films with sorbitol have higher ε\' values. The plasticized films with higher moisture content exhibit lower crystallinity, hence larger molecular mobility and consequently higher the relative permittivity.

L’identification par radio fréquence (RFID) connectée à des capteurs est une technologie grandissante pour les emballages intelligents. Ces travaux de thèse ont porté sur l’étude des propriétés électriques (impédance et capacité) et diélectriques (permittivité diélectrique et pertes) des protéines notamment le gluten de blé, en fonction des molécules environnementales connues comme des marqueurs de dégradation des denrées alimentaires. Les effets de ces molécules (eau, dioxyde de carbone et éthanol) sur les propriétés électriques et diélectriques du gluten de blé ont été analysés. Dans le but d’effectuer des mesures dans des conditions optimales, plusieurs étapes ont été mises en place:Le développement d’une méthode, permettant une haute exposition du gluten de blé à l’atmosphère environnant, afin d’acquérir des mesures électriques et diélectriques du gluten de blé dans des conditions contrôlées de température, vapeurs et de gaz ;L’analyse des effets des vapeurs et gaz sur les propriétés diélectriques du gluten de blé, ainsi que la détermination de différents paramètres tels que la sensibilité et l’hystérésis, propres aux capteurs ;L’enduction du gluten de blé sur une étiquette RFID, testée en fonction de l’humidité et dans des conditions réelles d’utilisation. Les effets sur la distance de lecture de l’étiquette RFID ont été analysés.Les résultats obtenus sont prometteurs au vu des modifications de la permittivité diélectrique et des pertes, indiquant une modification structurelle de la protéine, qui aurait un impact sur la réponse RFID. La permittivité diélectrique a été augmenté de 5.01±0.06 à 9.22±0.06, de 7.81±0.07 à 12.02±0.03 et de 6.66±0.01 à 11.77±0.01, pour une croissance de 20% à 95% de l’humidité relative, de 0% à 40% de dioxyde de carbone et de 0% à 0.1% d’éthanol respectivement, aboutissant à une sensibilité de 26.70±0.13fF/%RH,31.38±0.06fF/%CO2 et 25.50±0.05pF/%éthanol pour les 3 vapeurs et gaz. Les propriétés diélectriques du gluten et sa sensibilité aux vapeurs et aux gaz offrent de nouvelles perspectives sur la conception de capteurs à bas coûts et écologiques, connectés à des étiquettes RFID passives pour les emballages intelligents et pour le contrôle de la chaîne alimentaire. / Radio frequency identification (RFID) interfaced to sensors is a growing technology for intelligent packaging. The present thesis work is based on the study of the electrical (impedance and capacitance) and dielectric properties (dielectric permittivity and loss) of proteins principally wheat gluten, as a function of environmental molecules known as markers of food degradation. The impacts of those molecules (water, carbon dioxide and ethanol), usually found in food packages, on the electrical and dielectric properties of wheat glutenhave been investigated. In order to perform measurements in the optimum conditions, several steps have been set up:The development of a methodology, allowing a high exposure of wheat gluten to the surrounding atmosphere, offering the possibility to perform electrical measurements and identify dielectric properties of wheat gluten in controlled conditions of vapors and gases ;Analyzing the impact of vapors and gases on the dielectric properties of wheat gluten, and the determination of several parameters such as sensitivity and hysteresis, specific to sensors ;The coating of wheat gluten on a RFID tag, tested as a function relative humidity and in real conditions of use. The subsequent impacts on the reading range of the RFID tag have been analyzed.The results obtained are promising according to modifications of the dielectricpermittivity and loss, indicating a structural modification of the protein, sought to have an impact on the RFID response. The dielectric permittivity was increased from 5.01±0.06 to 9.22±0.06, from 7.81±0.07 to 12.02±0.03 and from 6.66±0.01 to 11.77±0.01, for an increase in relative humidity from 20% to 95%, in carbon dioxide from 0% to 40% and in ethanol from 0% to 0.1%, respectively, resulting in a sensitivity of 26.70±0.13fF/%RH, 31.38±0.06fF/%CO2 and 25.50±0.05pF/%ethanol for the 3 vapors and gases. The dielectric properties of wheat gluten and its sensitivity to vapors and gases offer new insights on theconception of low cost, eco-friendly sensors sought to be interfaced to passive RFID tags for intelligent packaging for food and supply chain monitoring.

Disorder in materials often brings in new and exotic physical properties along with it. It is thus very important to study different kinds of disorder and their implications on various material properties. In this thesis, we study selected transition metal oxide families of compounds, each being associated with a specific kind of disorder and investigate effects of that disorder on their dielectric and magnetic properties. In Chapter1, we have given brief introductions on the origin of magnetic and dielectric properties in materials and have also discussed various mechanism which give rise to multiferroism in materials which exhibit both spontaneous magnetic ordering and spontaneous electric ordering in the same phase of the material. In Chapter2,we describe the various methodologies adopted in this thesis. In Chapter3,we mainly study the effect of cationic size-disorder in deciding un-usually robust dielectric properties of Ln2CuTiO6(Ln=Y,Dy,Ho,Er,Yb) family of compounds. We discover that these materials, in addition to possessing large dielectric constant values, also exhibit exceptional stabilities of their dielectric constants with respect to large changes in temperature and frequency. We further find that this class of materials are non-ferroelectrics though its hares the same non-centrosymmetric space group, P63cm,with the well-known multiferroic YMnO3 that undergoes a ferroelectric transition at 940K. Using first principles calculations, we establish that exceptional dielectric properties result from a combination of two separate effects. Extensive size disorders at the Cu/Ti B-site suppress the expected ferroelectric transition, leading to relatively large values of the dielectric constant for every compound investigated in this series. Additionally, it is shown that the majority contribution to the dielectric constant arises from intermediate-frequency polar vibrational modes, making it relatively stable against temperature variations. In Chapter4, we study the effect of cation anti-site disorder on the magnetic, electric and dielectric properties of the solid solution series of (x)Fe2O3-(1-x)FeTiO3 for several values of x. For intermediate values of x, these solid solution members are found to be strong ferrimagnets. Anti-site cation disorder, between Fe and Ti, however strongly reduces the magnetic moment values. By tuning the degree of cation anti-site disorder, we attain multi-functionality in these samples. We have performed detailed characterizations of valence states of Fe and Ti across the solid solution series using x-ray photoelectron spectroscopy and x-ray absorption spectroscopy. Using x-ray magnetic circular dichroism, we validate the microscopic model of magnetism and suggest a microscopic picture of the anti-site cation disorder for these samples. In Chapter5,we study the effects of controlled chemical disorder in SrTiO3 lattice, by performing site-specific doping of Mn in SrTiO3. We find that site specific Mn doping has decisive influence on their dielectric properties with qualitatively and quantitatively different behaviors between these doped samples .Using electron paramagnetic resonance experiments, we establish the site specific doping of Mn in SrTiO3 lattice. We find that while Mn doping at Ti site continues to remain paraelectric, Mn doping at the Sr site becomes a relaxor ferroelectric. We find samples having Mn substituted at both Sr and Ti sites simultaneously to be also relaxor ferroelectrics. Combining experiments with first principles calculations, we understand the origin for the high temperature dielectric properties of various Mn doped SrTiO3 samples. We show that Mn ions doped at the Sr sites off-centers and gives a significant dipolar contribution to their dielectric constants. While demonstrating the superior dielectric properties of Mn doped SrTiO3 ceramics ,we also elucidate their magnetic properties in details. In Chapter6,we study the effect of cation anti-site disorder on the magnetic and dielectric properties of undoped and Lu doped La2NiMnO6 samples. Using detailed spectroscopic characterizations of these samples with x-ray absorption experiments, coupled with d.c.magnetization and a.c.susceptibility measurements, we demonstrate that while the doped samples are ferromagnetic, the undoped samples exhibit re-entrant spin-glass magnetism. We also show that the dielectric properties of undoped La2NiMnO6,crys-tallizing in monoclinic and rhombohedral phases are distinctly different and we study their dielectric relaxations in details. We also demonstrate multiferroism in Lu doped La2NiMnO6 samples. In Appendix A, we study the electronic origin of ferroelectric polarization in the spin spiral compound ,MnWO4. Using x-ray absorption spectroscopy on synthesized MnWO4 samples, coupled with configuration interaction calculations, we establish quantitatively a significant population of Mn 3d states beyond the expected half filling and provide a critical insight into the significant presence of spin-orbit coupling and consequent finite polarization in this system. In Appendix B, we study charge-transfer doping in few-layer grapheme covered with electron acceptor (Tetracyanoethylene) and donor (Tetrathiafulvalene) molecules using x-ray photoelectron spectroscopy. We give quantitative estimates of the extent of doping in these samples and thereby elucidate the origin of unusual shifts of their Raman G bands in contrast to electrochemically doping schemes. In conclusion, we investigate, in this thesis, properties of different classes of compounds in presence of distinctly different kinds of disorder and establish the critical role of disorder in each case in tuning their desirable physical properties.

Neste trabalho foi desenvolvido um dispositivo, denominado forno de indução eletromagnética (FIE), que permite trabalhar em altas temperaturas ~ 1900oC e com vácuo dinâmico equivalente a uma pressão parcial de oxigênio PO2 ~ 10-10 atm. Durante os experimentos de calibração do FIE, foram estudadas amostras de um composto binário de Y2O3 com 3% em mol de ZrO2, cujo pó foi obtido por mistura de óxidos. As amostras foram conformadas por prensagem uniaxial de 50 MPa, seguida de prensagem isostática a 350 MPa por 10 minutos e submetidas à sinterização em temperaturas superiores a 1800oC, resultando em transparência superior a 60% para comprimentos de onda em torno de 800 nm. Posteriormente, um composto quaternário de BaTi0.85Zr0.15O3 foi produzido por mistura de óxidos e calcinação a 1200oC. As amostras foram então conformadas seguindo a mesma metodologia da Y2O3, posteriormente sinterizadas entre 1250oC a 1400oC, com patamares de 1 h e 3 h. As amostras preparadas no FIE foram submetidas a uma pressão parcial de oxigênio de ~ 10-7 atm, enquanto outro conjunto de amostras foi sinterizado em um forno elétrico convencional (FEC) com atmosfera aberta para comparação. Foram realizadas caracterizações microestruturais aplicando-se as técnicas de difração de raios X, BET, EDX, microscopia eletrônica de varredura, além de caracterização elétrica por espectroscopia de impedância. Destas caracterizações verificou-se a obtenção de partículas do pó de BaTi0.85Zr0.15O3 com tamanho médio de 110 nm. O tamanho médio dos grãos nas microestruturas variou entre 4 e 30 &microm nas amostras fabricadas em FEC, enquanto nas amostras fabricadas em FIE o tamanho foi em torno de 250 nm. Para as amostras feitas no FEC, a resposta dielétrica dos grãos evidenciou o cumprimento da lei de Curie-Weiss conforme o modelamento bricklayer feito no programa Zview, porém foi observada anomalia dielétrica para medidas de permissividade em temperaturas maiores do que 96oC. O material feito no FIE não apresentou comportamento ferroelétrico no intervalo de temperatura estudado de -243 - 137oC, mas foi evidenciado um comportamento típico de material varistor. Considerando a relação entre as propriedades macro e microscópicas no modelo bricklayer, a ferroeletricidade e a variação da anomalia dielétrica são discutidas em função do tamanho de grãos para as amostras feitas no FEC. Com base no modelo de Pike para varistores, o comportamento varistor do material feito no FIE é discutido em função dos defeitos causados pela baixa pressão parcial de oxigênio ~ 10-7 atm. / In this work it has been developed a device, called electromagnetic induction furnace (EIF), which allow us to work at high temperatures ~ 1900oC and under dynamic vacuum equivalent to partial pressure of oxygen PO2 ~ 10-10 atm. During the calibration experiments of the EIF, it was studied a binary compound of Y2O3 with 3 mol% of ZrO2 which was obtained by mixing oxides. The samples were processed by uniaxial pressing 50 MPa followed by isostatic pressing at 350 MPa for 10 minutes and submitted to sintering at temperatures above 1800 oC, resulting in transparency greater than 60% for wavelengths around 800 nm. After, a quaternary compound of BaTi0.85Zr0.15O was produced by mixing oxides and calcination at 1200 oC. Then the samples were shaped according to the same methodology of the Y2O3 subsequently sintered between 1250oC to 1400 oC, with 1 h and 3 h baseline. The samples prepared in the EIF were submitted to oxygen partial pressure of ~ 10-7 atm, while another samples set was sintered in a conventional electric furnace (CEF) with open atmosphere for comparison. Microstructural characterizations were performed by applying the techniques of X-ray diffraction, BET, EDS, SEM, and electrical characterization by impedance spectroscopy. In these characterizations were obtained powder particles of BaTi0.85Zr0.15O3 with an average size of 110 nm. The average grain size in the microstructures ranged between 4 and 30 &microm in the samples fabricated in CEF, but in the samples manufactured in EIF the size has been around 250 nm. For samples made in the CEF, the dielectric response of the grains showed the fulfillment of the Curie-Weiss law according to the bricklayer model made in the Zview program, but was observed dielectric anomaly on measurements of permittivity at temperatures higher than 96 oC. The material made in EIF does not showed ferroelectric behavior in the studied temperature range -243 - 137 oC, but was shown a typical behavior of varistor material. Considering the relationship between macroscopic and microscopic properties in the bricklayer model, the ferroelectricity and the dielectric anomaly variation are discussed at function of the grain size for samples made in CEF. Based on the model of Pike for varistors, the varistor behavior of the material made in EIF is discussed in terms of defects caused by low oxygen partial pressure ~ 10-7 atm.

Efficient oil production and refining processes require the precise measurement of water content in oil (i.e., water-cut) which is extracted out of a production well as a byproduct. Traditional water-cut (WC) laboratory measurements are precise, but are incapable of providing real-time information, while recently reported in-line WC sensors (both in research and industry) are usually incapable of sensing the full WC range (0 – 100 %), are bulky, expensive and non-scalable for the variety of pipe sizes used in the oil industry. This work presents a novel implementation of a planar microwave T-resonator for fully non-intrusive in situ WC sensing over the full range of operation, i.e., 0 – 100 %. As opposed to non-planar resonators, the choice of a planar resonator has enabled its direct implementation on the pipe surface using low cost fabrication methods. WC sensors make use of series resonance introduced by a λ/4 open shunt stub placed in the middle of a microstrip line. The detection mechanism is based on the measurement of the T-resonator’s resonance frequency, which varies with the relative percentage of oil and water (due to the difference in their dielectric properties). In order to implement the planar T-resonator based sensor on the curved surface of the pipe, a novel approach of utilizing two ground planes is proposed in this work. The innovative use of dual ground planes makes this sensor scalable to a wide range of pipe sizes present in the oil industry. The design and optimization of this sensor was performed in an electromagnetic Finite Element Method (FEM) solver, i.e., High Frequency Structural Simulator (HFSS) and the dielectric properties of oil, water and their emulsions of different WCs used in the simulation model were measured using a SPEAG-dielectric assessment kit (DAK-12). The simulation results were validated through characterization of fabricated prototypes. Initial rapid prototyping was completed using copper tape, after which a novel reusable 3D-printed mask based fabrication was also successfully implemented, which would resemble screen printing if it were to be implemented in 3D. In order to verify the design’s applicability for the actual scenario of oil wells, where an oil/water mixture is flowing through the pipes, a basic flow loop was constructed in the IMPACT laboratory at KAUST. The dynamic measurements in the flow loop showed that the WC sensor design is also equally applicable for flowing mixtures. The proposed design is capable of sensing the WC with a fine resolution due to its wide sensing range, in the 80 – 190 MHz frequency band. The experimental results for these low cost and conformal WC sensors are promising, and further characterization and optimization of these sensors according to oil field conditions will enable their widespread use in the oil industry.

At the beginning, this master thesis briefly describes the principle of semiconductors. It states their types, methods of operation, fields of use, and it interprets the manner of semiconductor devices’ passivation. Then it introduces silicones, their properties and usage. Later on, this thesis summerize air humidity theory and materiál moisturing including mathematical interpretation. Next chapter is devoted to basics of dielectric materials’ behavior. And finally, the last part of this thesis estimates charakteristics of passivation materiál, Dow Corning HIPEC Q1-9205 silicone rubber.

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

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

In this dissertation, methods utilizing matched illumination theory to optimally design waveforms for enhanced target detection and identification in the context of through-the-wall radar (TWR) are explored. The accuracy of assumptions made in the waveform design process is evaluated through simulation. Additionally, the moisture profile of an adobe wall is investigated, and it is shown that the moisture profile of the wall will introduce significant variations in the matched illumination waveforms and subsequently, affect the resulting ability of the radar system to correctly identify and detect a target behind the wall. Experimental measurements of adobe wall moisture and corresponding dielectric properties confirms the need for accurate moisture profile information when designing radar waveforms which enhance signal-to-interference-plus-noise ratio (SINR) through use of matched illumination waveforms on the wall/target scenario. Furthermore, an evaluation of the ability to produce an optimal, matched illumination waveform for transmission using simple, common radar systems is undertaken and radar performance is evaluated.

No description available.