This thesis is devoted to an experimental study of dielectric properties of incipient fer- roelectrics. The terahertz time-domain spectroscopy was used to investigate the complex permittivity spectra in both single crystals and various strained thin film structures versus temperature and applied electric bias. Namely, it allowed characterizing the ferroelectric soft-mode dynamics and its coupling to a central mode. An electric-field tunability of bulk single crystals of SrTiO3 was determined up to room temperature for the first time. The phenomenon is governed by soft-mode stiffening under applied field. As an application we proposed and characterized a tunable one-dimensional photonic structure with a thin SrTiO3 plate inserted as a defect layer. The importance of the soft-mode dynamics was stressed also in the study of bulk high density KTaO3 ceramics. A systematic study was performed of a KTaO3 thin film and especially of a set of strained multilayers consisting of SrTiO3/DyScO3 bilayers grown on DyScO3 substrate. Strain-induced ferroelectric transition was observed in these films governed by the soft mode coupled to a lower-frequency relaxation. A general model was developed describing the whole family of the studied samples. Effect of the composition stoichiometry of SrTiO3 films grown on DyScO3 was...

A flexible nanofibrous PVDF-BaTiO3 composite material is prepared for impact sensing and biomechanical energy harvesting applications. Dielectric polyvinylidene fluoride (PVDF) and barium titanate (BaTiO3)-PVDF nanofibrous composites were made using the electrospinning process based on a design of experiments approach. The ultrasonication process was optimized using a 2k factorial DoE approach to disperse BaTiO3 particles in PVDF solution in DMF. Scanning electron microscopy was used to characterize the microstructure of the fabricated mesh. The FT-IR and Raman analysis were carried out to investigate the crystal structure of the prepared mesh. Surface morphology contribution to the adhesive property of the composite was explained through contact angle measurements. The capacitance of the prepared PVDF- BaTiO3 nanofibrous mesh was a more than 40% increase over the pure PVDF nanofibers. A comparative study of dielectric relaxation, thermodynamics properties and impact analysis of electrospun polyvinylidene fluoride (PVDF) and 3% BaTiO3-PVDF nanofibrous composite are presented. The frequency dependent dielectric properties revealed micro structural features of the composite material. The dielectric relaxation behavior is further supported by complex impedance analysis and Nyquist plots. The temperature dependence of electric modulus shows Arrhenius type behavior. The observed non-Debye dielectric relaxation in electric loss modulus follows a thermally activated process which can be attributed to a small polaron hopping effect. The particle induced crystallization is supported with thermodynamic properties from differential scanning calorimetric (DSC) measurements. The observed increase in piezoelectric response by impact analysis was attributed to the interfacial interaction between PVDF and BaTiO3. The interfacial polarization between PVDF and BaTiO3 was studied using density functional theory calculations and atomic charge density analysis. The results obtained indicates that electrospinning offers a potential way to produce nanofibers with desired crystalline nature which was not observed in molded samples. In addition, BaTiO3 can be used to increase the capacitance, desired surface characteristics of the PVDF nanofibers which can find potential application as flexible piezoelectric sensor mimicking biological skin for use in impact sensing and energy harvesting applications.

Hafnium oxide is widely used for resistive switching devices, and recently it has been discovered that ferroelectricity can be established in (un-)doped hafnium oxide as well. Previous studies showed that both switching mechanisms are influenced by oxygen vacancies. For resistive switching, typically amorphous oxide layers with an asymmetric electrode configuration are used to create a gradient of oxygen vacancies. On the other hand, ferroelectric switching is performed by having symmetric electrodes and requires crystalline structures. The coexistence of both effects has recently been demonstrated. In this work, a detailed analysis of the reversible interplay of both switching mechanisms within a single capacitor cell is investigated. First, ferroelectric switching cycles were applied in order to drive the sample into the fatigued stage characterized by increased concentration of oxygen vacancies in the oxide layer. Afterwards, a forming step that is typical for the resistive switching devices was utilized to achieve a soft breakdown. In the next step, twofold alternation between the high and low resistance state is applied to demonstrate the resistive switching behavior of the device. Having the sample in the high resistance state with a ruptured filament, ferroelectric switching behavior is again shown within the same stack. Interestingly, the same endurance as before was observed without a hard breakdown of the device. Therefore, an effective sequence of ferroelectric—resistive—ferroelectric switching is realized. Additionally, the dependence of the forming, set, and reset voltage on the ferroelectric cycling stage (pristine, woken-up and fatigued) is analyzed giving insight into the physical device operation.

Transient negative capacitance effects in epitaxial ferroelectric Pb(Zr₀.₂Ti₀.₈)O₃ capacitors are investigated with a focus on the dynamical switching behavior governed by domain nucleation and growth. Voltage pulses are applied to a series connection of the ferroelectric capacitor and a resistor to directly measure the ferroelectric negative capacitance during switching. A time-dependent Ginzburg-Landau approach is used to investigate the underlying domain dynamics. The transient negative capacitance is shown to originate from reverse domain nucleation and unrestricted domain growth. However, with the onset of domain coalescence, the capacitance becomes positive again. The persistence of the negative capacitance state is therefore limited by the speed of domain wall motion. By changing the applied electric field, capacitor area or external resistance, this domain wall velocity can be varied predictably over several orders of magnitude. Additionally, detailed insights into the intrinsic material properties of the ferroelectric are obtainable through these measurements. A new method for reliable extraction of the average negative capacitance of the ferroelectric is presented. Furthermore, a simple analytical model is developed, which accurately describes the negative capacitance transient time as a function of the material properties and the experimental boundary conditions.

[ES] La utilización de sistemas de microondas para aplicaciones de calentamiento está muy extendida, principalmente por su uso en el calentamiento doméstico. El volumen de ventas del horno de microondas doméstico refleja un dato curioso: es el electrodoméstico más vendido en el mundo cada año. Por ello, el coste de producción del elemento principal, el magnetrón, presenta unos márgenes de beneficio imbatibles. Sin embargo, los avances en la fabricación de generadores de RF de alta potencia de estado sólido han puesto de manifiesto no solo las limitaciones de los sistemas basados en magnetrón sino también las grandes ventajas de la tecnología de transistores. Actualmente, los amplificadores de potencia de estado sólido han alcanzado una madurez suficiente como para competir en eficiencia, coste y calidad de la onda generada con el magnetrón. Las principales ventajas de los transistores son un reducido tamaño, tensiones de alimentación bajas, un espectro puro en frecuencia, un mayor tiempo de vida y el control digital directo. Los sistemas de microondas con esta tecnología están siendo introducidos en el mercado desde hace diez años, aunque las aplicaciones reales que los utilizan son escasas. La principal razón es la falta de diseños de aplicadores específicos para sacar el máximo provecho a las fuentes de estado sólido. , por tanto, es éste el objetivo de la tesis doctoral. Los sistemas S2MH (Solid-State Microwave Heating) se presentan en esta disertación doctoral como una alternativa que ofrece un calentamiento mejorado. La posibilidad de seleccionar la frecuencia exacta, ajustar la potencia de salida y realizar barridos de fase de forma coherente con múltiples iluminadores proporcionan al sistema un control preciso del proceso de calentamiento. El resultado directo de éste es un calentamiento homogéneo y el uso de la tecnología de microondas en procesos de alto valor añadido y fuerte dependencia con la temperatura. Esta tesis doctoral presenta el trabajo realizado en el diseño y fabricación de dos sistemas S2MH: el primero es un horno estático versátil para diferentes procesos químicos, y el segundo un horno de transporte para el secado de almendras. Estos dos sistemas están formados por el SSMGS (Solid-State Microwave Generator System), que incluye cuatro amplificadores de estado sólido (SSPA) con una generación de la onda coherente, y el aplicador. Para el diseño del SSMGS se han tenido en cuenta los requisitos de potencia y frecuencia de cada aplicación. Se ha utilizado un SSMGS con cuatro PA de 250 W a 2,450 MHz para el horno de aplicaciones químicas, mientras que el secado de almendras necesita cuatro PA de 500 W a 915 MHz. Los dos sistemas de generación de microondas permiten un control individual o combinado de los parámetros de los cuatro módulos amplificadores, i.e., potencia, frecuencia y fase. Todo el proceso de diseño ha sido llevado a cabo mediante modelado multi-físico, poniendo un especial cuidado en las propiedades termofísicas y dieléctricas de los alimentos y soluciones acuosas que tienen una importante dependencia con la temperatura. El comportamiento completo del sistema aplicador se ha estudiado con estas herramientas. Tras la fabricación de los dos prototipos o pruebas de concepto (PoC), los resultados obtenidos presentan un comportamiento similar al modelo y muestran, además, prometedoras mejoras frente a los sistemas actuales. El sistema de aplicaciones químicas presenta mejoras en la distribución de campo, independientemente de la aplicación y la carga. Y el sistema de secado de almendras proporciona un mayor control sobre el proceso evitando la pérdida de material por sobrecalentamiento. / [CA] La utilització de sistemes de microones en aplicacions d'escalfament està molt estesa, principalment pel seu us en escalfament domèstic. El volum de ventes del forn de microones domèstic reflexa una informació curiosa: es l'electrodomèstic més venut anualment al món. Per això, el cost de producció del seu element principal, el magnetró, presenta uns marges de benefici imbatibles. No obstant això, els avanços en la fabricació de generadors de RF d'alta potencia d'estat sòlid han posat de manifest tant les limitacions dels sistemes basats en magnetró, com els grans avantatges de la tecnologia de transistors. Actualment, els amplificadors de potència d'estat sòlid son el suficientment madurs com per competir en eficiència, cost i qualitat de l'ona generada amb el magnetró. Els principals avantatges dels transistors son les dimensions reduïdes, tensions d'alimentació baixes, un espectre pur en freqüència, major temps de vida i el control digital directe. Els sistemes de microones amb aquesta tecnologia estan sent introduïts al mercat des de fa deu anys, malgrat les aplicacions reals son escasses. El principal motiu és la falta de dissenys de aplicadors específics per obtindré el màxim profit de les fonts d'estat sòlid. , por tanto, es éste el objetivo de la tesis doctoral. Els sistemes S2MH es presenten en esta dissertació doctoral com una alternativa que ofereix un escalfament millorat. La possibilitat de seleccionar la freqüència exacta, ajustar la potència d'eixida i realitzar un rastreig de fase de forma coherent amb molts il·luminadors proporcionen al sistema un control precís del procés d'escalfament. El resultat directe d'aquest es un escalfament homogeni i el us de la tecnologia de microones en processos d'alt valor afegit i alta sensibilitat a la temperatura. Aquesta dissertació doctoral presenta el treball realitzat en el disseny i fabricació de dos sistemes S2MH: el primer és un forn estàtic i versàtil per a diferent processos químics, i el segon es tracta d'un forn de transport per l'assecatge d'ametles. Tots dos sistemes estan formats pel SSMGS, que inclou quatre amplificadors d'estat sòlid (SSPA) amb generació coherent de l'ona, i l'aplicador. Per al disseny del SSMGS s'han tingut en compte els requisits de potència i freqüència de cada aplicació. S'ha utilitzat un SSMGS amb quatre PA de 250 W a 2,450 MHz per al forn d'aplicacions químiques, mentre que per al d'assecat d'ametla es necessita quatre PA de 500 W a 915 MHz. Ambdós sistemes de generació de microones permeten un control individual o combinat dels paràmetres dels quatre mòduls amplificadors, i.e., potència, freqüència i fase. Tot el procés de disseny ha sigut realitzat amb l'ajuda del modelat multi-físic, prestant una especial atenció a les propietats termofísiques i dielèctriques dels aliments i solucions aquoses, que tenen una important dependència de la temperatura. El comportament complet del sistema aplicador ha sigut estudiat amb estes ferramentes digitals. Després de la fabricació dels dos prototips o proves de concepte (PoC), els resultats obtinguts presenten un comportament similar al model i, a més a més, mostren millores prometedores front als sistemes actuals. El sistema d'aplicacions químiques presenta millores en la distribució de camp, independentment de l'aplicació i la càrrega. I el sistema d'assecatge d'ametlles proporciona un major control sobre el procés, evitant la pèrdua de material per sobreescalfament. / [EN] Microwave systems are widely used for heating applications, mainly domestic food heating. The microwave oven sales figures place it as the first domestic appliance, giving its core element, the magnetron, an unbeatable production cost margin. However, recent improvements in RF high-power generator manufacturing have pointed out not only the limitations of these systems based on the magnetron but also the main benefits of the transistors technology. Nowadays, solid-state power amplifiers are mature enough to compete in efficiency, cost and quality with the magnetron. Transistors' main benefits are their reduced size, low operation voltages, pure frequency spectrum, lifetime, and straightforward digital control. Microwave systems based on solid-state power amplifiers have been recently introduced, although the real applications making use of them are rare. The main issue is the lack of applicator designs for specific solid-state sources that fully exploit the mentioned advantages; therefore, this is the main objective of the present PhD thesis. Solid-State Microwave Heating (S2MH) systems are presented in this PhD dissertation as an alternative that offers enhanced heating. Fine frequency selection, adjustable output power and coherent phase sweep in multiple outputs provide the system with accurate control over the heating process. The direct outcome of this control is the production of homogeneous heating and the application of microwave technology into high-added-value temperature-sensitive processes. The complete design and manufacture of two S2MH systems have been carried out and presented in this PhD thesis. The two designed systems are a multi-process chemical lab batch oven and an almond drying conveyorized oven. These two systems are composed of the Solid-State Microwave Generator System (SSMGS), consisting of four Solid-State Power Amplifiers (SSPA) with coherent wave generation, and the applicator. The design of the SSMGS has been carried out according to the power and frequency requirements of the application. A 4 x 250 W SSPA at 2,450 MHz SSMGS has been used for the chemical processes oven, while the almond drying application needs 4 x 500 W SSPA at 915 MHz. Both SSMGS allow the individual or combined digital control of the parameters of the four amplifying modules, i.e., power, frequency and phase. Multiphysics modelling has been thoroughly studied with special attention to the temperature-dependent thermophysical and dielectric properties of food and liquid solutions. The overall applicators' behaviour has been analysed with this tool. After completing the two PoC (Proof of Concept), the results show good agreement with the models. Both PoCs have shown promising improvements to the current state-of-the-art systems. The chemical applications PoC shows electromagnetic field distribution improvements, independent of the application or load. On the other hand, the almonds drying system provides increased control over the process avoiding material losses through overheating. / Santón Pons, P. (2022). Design and Development of a Multi-Frequency System for Microwave Heating [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/191326

Manifold research has been done to understand the detailed mechanisms behind the performance instabilities of ferroelectric capacitors based on hafnia. The wake-up together with the imprint might be the most controversially discussed phenomena so far. Among crystallographic phase change contributions and oxygen vacancy diffusion, electron trapping as the origin has been discussed recently. In this publication, we provide evidence that the imprint is indeed caused by electron trapping into deep states at oxygen vacancies. This impedes the ferroelectric switching and causes a shift of the hysteresis. Moreover, we show that the wake-up mechanism can be caused by a local imprint of the domains in the pristine state by the very same root cause. The various domain orientations together with an electron trapping can cause a constriction of the hysteresis and an internal bias field in the pristine state. Additionally, we show that this local imprint can even cause almost anti-ferroelectric like behavior in ferroelectric films.

The Rayleigh law describes the linear dependence of the permittivity of a ferroelectric on the applied ac electric field amplitude due to irreversible motions of domain walls. We show that this gives rise to a new equivalent-circuit element predestined to fit the impedance spectra of ferroelectrics based on an accepted physical model. Such impedance spectroscopy is a powerful tool to obtain a dielectric and resistive representation of the entire sample structure. The superiority of the Rayleigh analysis based on impedance spectroscopy compared to the common single-frequency approach is demonstrated for a ferroelectric Si : HfO₂ thin film

Tesis por compendio / [ES] La permitividad es una propiedad física de los materiales que describe su comportamiento en presencia de un campo electromagnético. Los sensores de microondas pueden desempeñar un papel esencial en las tareas de detección, supervisión o control de procesos, ya que algunos parámetros fisicoquímicos de los materiales producen cambios medibles en las propiedades dieléctricas. Además, la tecnología de calentamiento por microondas está adquiriendo una relevancia creciente para la transición ecológica y la descarbonización de los procesos industriales, y la permitividad es el parámetro esencial para el desarrollo exitoso de estos nuevos procesos. La permitividad depende de muchos factores, por lo que los métodos de medición de la permitividad deben adaptarse a las necesidades del material y del entorno de medición. El número de aplicaciones que requieren la monitorización o medida de las propiedades dieléctricas, las altas dependencias de esta magnitud bajo diferentes condiciones, y la necesidad de poner esta tecnología al alcance de un usuario más amplio y menos especializado, justifican el desarrollo de este trabajo. Esta tesis pretende desarrollar nuevos dispositivos para la monitorización y caracterización de dieléctricos adaptados a diferentes entornos, cubriendo un amplio rango de formatos, formas y propiedades de los materiales. Las dos primeras publicaciones incluidas en la tesis describen dos enfoques diferentes para abordar las mediciones de permitividad. El primer artículo describe un instrumento versátil, autónomo y fácil de usar para medir la permitividad de materiales dentro de tubos. El diseño de la cavidad logró una excelente sensibilidad, y el estudio de la red de acoplamiento permitió la caracterización de materiales de pérdidas bajas, moderadas y altas con una misma configuración. Este dispositivo incluye un reflectómetro vectorial portátil propio, lo que lo hace portátil y asequible. Las características del instrumento desarrollado permiten un uso sencillo por parte de personal no especializado y proporcionan versatilidad en muchas situaciones. La segunda publicación presenta el diseño específico de una sonda coaxial de extremo abierto con una mayor sensibilidad para determinar la permitividad de productos alimenticios de altas pérdidas en función de la temperatura a frecuencias de RF. Este artículo destaca la importancia de seleccionar la técnica de medición más adecuada, adaptada al entorno y a las particularidades del material, para la determinación apropiada de la permitividad. Los dos artículos siguientes describen el desarrollo y la utilización de un microscopio de microondas de campo cercano con resolución micrométrica para determinar mapas de permitividad de materiales planos heterogéneos a frecuencias de microondas. En ambos trabajos se describen los diferentes elementos que componen el instrumento del microscopio y las técnicas de análisis para determinar los valores de permitividad a partir de las medidas de los parámetros de la resonancia. En el primer trabajo se empleó por primera vez la tecnología de microondas en aplicaciones contra la falsificación, obteniendo la marca dieléctrica de la marca de agua de un billete. Además, este estudio demostró la capacidad de la energía de microondas para detectar marcas ocultas detrás de capas dieléctricas o metálicas, lo que abre nuevas posibilidades para el desarrollo de elementos de seguridad ópticamente opacos e imposibles de rastrear por medios ópticos. El segundo estudio demuestra la versatilidad de este sistema para determinar las propiedades dieléctricas de materiales planos heterogéneos midiendo la respuesta dieléctrica de especímenes de roca. Los métodos desarrollados en esta tesis aumentan la cartera de sistemas de caracterización dieléctrica y pueden ayudar a una amplia gama de sectores científicos e industriales en las tareas de monitorización y caracterización dieléctrica, haciendo estos trabajos más cómodos y accesibles. / [CA] La permitivitat és una propietat física dels materials que descriu el seu comportament en presència d'un camp electromagnètic. Els sensors de microones poden exercir un paper essencial en les tasques de detecció, supervisió o control de processos, ja que alguns paràmetres fisicoquímics dels materials produeixen canvis mesurables en les propietats dielèctriques. A més, la tecnologia de calfament per microones està adquirint una rellevància creixent per a la transició ecològica i la descarbonització dels processos industrials, i la permitivitat és el paràmetre essencial per al desenvolupament reeixit d'aquests nous processos. La permitivitat depén de molts factors i, per tant, els mètodes de mesurament de la permitivitat han d'adaptar-se a les necessitats del material i de l'entorn de mesurament. El nombre d'aplicacions que requereixen el monitoratge o mesura de les propietats dielèctriques, les altes dependències d'aquesta magnitud sota diferents condicions, i la necessitat de posar aquesta tecnologia a l'abast d'un usuari més ampli i menys especialitzat, justifiquen el desenvolupament d'aquest treball. Aquesta tesi pretén desenvolupar nous dispositius per al monitoratge i caracterització de dielèctrics adaptats a diferents entorns, cobrint un ampli rang de formats, formes i propietats dels materials. Les dues primeres publicacions incloses en la tesi descriuen dos enfocaments diferents per a abordar els mesuraments de permitivitat. El primer article descriu un instrument versàtil, autònom i fàcil d'usar per a mesurar la permitivitat de materials dins de tubs. El disseny de la cavitat va aconseguir una excel·lent sensibilitat, i l'estudi de la xarxa d'acoblament va permetre la caracterització de materials de pèrdues baixes, moderades i altes amb una mateixa configuració. Aquest dispositiu inclou un reflectòmetre vectorial portàtil propi, la qual cosa el fa portàtil i assequible. Les característiques de l'instrument desenvolupat permeten un ús senzill per part de personal no especialitzat i proporcionen versatilitat en moltes situacions. La segona publicació presenta el disseny específic de una sonda coaxial d'extrem obert amb una major sensibilitat per a determinar la permitivitat de productes alimentaris d'altes pèrdues en funció de la temperatura a freqüències de RF. Aquest article destaca la importància de seleccionar la tècnica de mesurament més adequat, adaptada a l'entorn i a les particularitats del material, per a la determinació apropiada de la permitivitat. Els dos articles següents descriuen el desenvolupament i la utilització d'un microscopi de microones de camp pròxim amb resolució micromètrica per a determinar mapes de permitivitat de materials plans heterogenis a freqüències de microones. En tots dos treballs es descriuen els diferents elements que componen l'instrument del microscopi i les tècniques d'anàlisis per a determinar els valors de permitivitat a partir de les mesures dels paràmetres de la ressonància. En el primer treball es va emprar per primera vegada la tecnologia de microones en aplicacions contra la falsificació, obtenint la marca dielèctrica de la marca d'aigua d'un bitllet. A més, aquest estudi va demostrar la capacitat de l'energia de microones per a detectar marques ocultes darrere de capes dielèctriques o metàl·liques, la qual cosa obri noves possibilitats per al desenvolupament d'elements de seguretat òpticament opacs i impossibles de rastrejar per mitjans òptics. El segon estudi demostra la versatilitat d'aquest sistema per a determinar les propietats dielèctriques de materials plans heterogenis mesurant la resposta dielèctrica d'espècimens de roca. Els mètodes desenvolupats en aquesta tesi augmenten la cartera de sistemes de caracterització dielèctrica i poden ajudar a una àmplia gamma de sectors científics i industrials en les tasques de monitoratge i caracterització dielèctrica, fent aquests treballs més còmodes i accessibles. / [EN] Permittivity is a physical property of materials describing their behavior in the presence of an electromagnetic field. Microwave sensors can play an essential role in detecting, monitoring, or process control tasks as some physicochemical parameters of materials produce measurable changes in dielectric properties. Besides, microwave heating technology is gaining increasing relevance for the ecological transition and decarbonization of industrial processes, and permittivity is the essential parameter for the successful development of these new processes. Permittivity depends on many factors and thus, permittivity measurement methods must be adapted to the needs of the material and the measurement environment. The number of applications that require the monitoring or measurement of dielectric properties, the high dependencies of this magnitude under different conditions, and the need to make this technology available to a broader and less specialized user justify the development of this work. This thesis aims to develop new devices for the monitoring and characterization of dielectrics adapted to different environments, covering a wide range of materials' formats, shapes, and properties. The first two publications included in the thesis describe two different approaches to address permittivity measurements. The first paper describes a versatile, stand-alone, and easy-to-use instrument for measuring the permittivity materials inside tubes. The design of the cavity achieved an excellent sensitivity, and the study of the coupling network allowed the characterization of low, moderate, and high-loss materials with the same setup. This device included an in-house portable vector reflectometer, making it portable and cost-affordable. The features of the developed instrument allow straightforward use by non-specialized personnel and provide versatility in many situations. The second publication presents a specific open-ended coaxial design with increased sensitivity to determine the permittivity of lossy food products as a function of temperature at RF frequencies. This paper highlight the relevance of selecting the most suitable measurement technique, adapted to the environment and particularities of the material, for the appropriate determination of permittivity. The following two papers describe the development and use of a near-field scanning microwave microscope with micrometric resolution to determine permittivity maps of heterogeneous planar materials at microwave frequencies. The different elements comprising the microscope instrument and the analysis techniques to determine permittivity values from the resonance measurements were described throughout both works. In the first paper, microwave technology was employed for the first time in anti-counterfeiting applications by obtaining the dielectric mark of a banknote watermark. Besides, this study showed the ability of microwave energy to detect hidden marks behind dielectric or metallic layers, opening new possibilities for developing optically opaque security features untraceable by optical means. The second study demonstrates the versatility of this system in determining the dielectric properties of heterogeneous planar materials by measuring the dielectric response of rock specimens. The methods developed in this thesis dissertation increase the portfolio of dielectric characterization systems and can help a wide range of scientific and industrial sectors in dielectric monitoring and characterization tasks, making these works more convenient and accessible. / Financial support through the grant reference BES-2016-077296 of the call Convocatoria de las ayudas para contratos predoctorales para la formación de doctores de 2016 by Ministerio de Economía y Competitividad (MINECO) and by European Social Funds (ESF) of European Union is also gratefully acknowledged / Gutiérrez Cano, JD. (2022). Microwave Dielectrometry Adapted to Environments [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/186351 / TESIS / Compendio

There is great interest in the development of new polar dielectric ceramics and multiferroic materials with new and improved properties. A family of tetragonal tungsten bronze (TTB) relaxors of composition Ba₆M³⁺Nb₉O₃₀ (M³⁺ = Ga³⁺, Sc³⁺ and In³⁺, and also their solid solutions) were studied in an attempt to understand their dielectric properties to enable design of novel polar TTB materials. A combination of electrical measurements (dielectric and impedance spectroscopy) and powder diffraction (X-ray and neutron) studies as a function of temperature was employed for characterising the dynamic dipole response in these materials. The effect of B-site doping on fundamental dipolar relaxation parameters were investigated by independently fitting the dielectric permittivity to the Vogel-Fulcher (VF) model, and the dielectric loss to Universal Dielectric Response (UDR) and Arrhenius models. These studies showed an increase in the characteristic dipole freezing temperature (T[subscript(f)]) with increase B-cation radius. Crystallographic data indicated a corresponding maximum in tetragonal strain at T[subscript(f)], consistent with the slowing and eventual freezing of dipoles. In addition, the B1 crystallographic site was shown to be most active in terms of the dipolar response. A more in-depth analysis of the relaxor behaviour of these materials revealed that, with the stepwise increase in the ionic radius of the M³⁺ cation on the B-site within the Sc-In solid solution series, the Vogel-Fulcher curves (lnf vs. T[subscript(m)]) are displaced to higher temperatures, while the degree of relaxor behaviour (frequency dependence) increases. Unfortunately, additional features appear in the dielectric spectroscopy data, dramatically affecting the Vogel-Fulcher fitting parameters. A parametric study of the reproducibility of acquisition and analysis of dielectric data was therefore carried out. The applicability of the Vogel-Fulcher expression to fit dielectric permittivity data was investigated, from the simple unrestricted (“free”) fit to a wider range of imposed values for the VF relaxation parameters that fit with high accuracy the experimental data. The reproducibility of the dielectric data and the relaxation parameters obtained by VF fitting were shown to be highly sensitive to the thermal history of samples and also the conditions during dielectric data acquisition (i.e., heating/cooling rate). In contrast, UDR analysis of the dielectric loss data provided far more reproducible results, and to an extent was able to partially deconvolute the additional relaxation processes present in these materials. The exact nature of these additional relaxations is not yet fully understood. It was concluded application of the Vogel-Fulcher model should be undertaken with great care. The UDR model may represent a feasible alternative to the evaluation of fundamental relaxation parameters, and a step forward towards the understanding of the dielectric processes in tetragonal tungsten bronzes.

The challenges of measuring speech signals in the presence of a strong background noise cannot be easily addressed with traditional acoustic technology. A recent solution to the problem considers combining acoustic sensor measurements with real-time, non-acoustic detection of an aspect of the speech production process. While significant advancements have been made in that area using low-power radar-based techniques, drawbacks inherent to the operation of such sensors are yet to be surmounted. Therefore, one imperative scientific objective is to devise new, non-invasive non-acoustic sensor topologies that offer improvements regarding sensitivity, robustness, and acoustic bandwidth. This project investigates a novel design that directly senses the glottal flow waveform by measuring variations in the electromagnetic properties of neck tissues during voiced segments of speech. The approach is to explore two distinct sensor configurations, namely the“six-element" and the“parallel-plate" resonator. The research focuses on the modeling aspect of the biological load and the resonator prototypes using multi-transmission line (MTL) and finite element (FE) simulation tools. Finally, bench tests performed with both prototypes on phantom loads as well as human subjects are presented.