Thesis (MEng)--Stellenbosch University, 2014. / ENGLISH ABSTRACT: Over the past 50 years smart materials have made their appearance in many structures. The thermopiezoelectric ceramic is one of these smart materials. When thermal e ects are considered negligible, then the materials are classified as piezo-ceramic and piezoelectric materials. These so called piezo-ceramics are used as actuator and sensor components in many structures. The use of these components with composite materials is significant due to their application in the aerospace and aeronautics fields. The interaction that the piezoelectric material has with a composite body can be improved in order to reduce the energy requirement of the material for deformation. An objective in the optimisation of composite material structures is to minimise compliance or maximise sti ness uT f, with the laminate ply orientations as design variables, where u and f are displacement and force vectors, respectively. Here, the objective is not the maximisation of sti ness but the maximisation of compliance, with typical constraints being failure criteria. These failure criteria can include theories such as the maximum principle stress, the Tsai-Hill or Tsai-Wu failure theories. The compliance is maximised to accentuate any piezoelectric movement and is for theoretical treatment only. Piezoelectric materials once polarized the materials becomes quasi-isotropic. The piezoelectric materials are isotropic in the plane normal to the direction of the voltage being applied and have altered properties normal to this plane. This change in the material properties can be exploited so that the layup can be altered in orientation to improve performance. The idea is to improve the mechanical capabilities of the structure subject to an electrical input or vice versa. In the works by both Carrera et al. and Piefort, First Order Shear Deformation Theory (FSDT) is used in finite element analysis to characterise the structural and electrical behaviour of a plate or shell. FSDT, also known as the Mindlin-Reissner theory, is a plate bending theory that assumes a transverse shear distribution through the thickness of the plate. This theory is considered an improvement on the standard theories such as the Kircho or Timoshenko theories. Many optimisation techniques exist and are classed as either being direct search or gradient based methods. Particle Swarm Optimisation (PSO) is a direct search method. It mimics the behaviour of a flock of birds or school of fish in their attempt to find food. The PSO’s mathematical statement characterises a set of initial unknown particles within a designated search space that are compared to a set of local best particles and a single global best particle. This comparison is used to update the swarm each run cycle. Regression is a procedure whereby a set of testing data is used to fit a pseudo-function that represents the form the data should take in practice. The aim of this work is to optimise the piezoelectric-composite layer interaction to improve the overall compliance of a structure. Extensive modelling is performed and tested with peer reviewed literature to demonstrate its accuracy. / AFRIKAANSE OPSOMMING: Oor die afgelope 50 jaar het slim materiale hulle verskyning gemaak in verskeie strukture. Termopiezo-elektriese keramieke is een van hierdie nuwe materiale. Wanneer termiese e ekte onbeduidend is, word hierdie materiale as piezo-elektriese materiale geklassifiseer. Hierdie sogenaamde piezo-keramieke word gebruik as aandrywers en sensoriese onderdele in verskeie strukture. Die kombinasie van hierdie onderdele met saamgestelde materiale het belangrike toepassings in die ruimte- en lugvaartkunde. Die interaksie van die piezo-elektriese materiale met die saamgestelde materiaal strukture kan verbeter word om die energie-vereistes van die materiaal vir vervorming te verminder. ’n Tipiese doel in die optimering van saamgestelde materiaalstrukture is om styfheid uT f te maksimeer met die gelamineerde laag-oriëntasies as ontwerpsveranderlikes, waar u en f onderskeidelik verplasing en kragvektor voorstel. In teenstelling met die optimering van die samestelling wat voorheen gedoen is, is die doel hier nie die maksimering van styfheid nie, maar die minimering van styfheid, met falingskriteria as tipiese beperkings. Die falingskriteria sluit die volgende in: die maksimum spanningsteorie, en die Tsai-Hill of Tsai-Wu falingsteorieë. Die styfheid word geminimeer om piezo-elektriese verplasing te versterk, maar word hierin net teoreties bekyk. Sodra piezo-elektriese materiale gepolariseer word, word hulle quasi-isotropies. Die piezoelektriese materiale is isotropies in die vlak gelyk aan die rigting van die stroomspanning wat daarop toegepas word en het ander eienskappe normaal tot die vlak. Die verandering in die materiaal se eienskappe kan gebruik word sodat beide die saamgestelde materiaal en die piezoelektriese laag se oriëntasie aangepas kan word vir verbeterde werkverrigting. Die idee is om die meganiese vermoëns te verbeter van ’n struktuur wat onderwerp word aan ’n elektriese inset of vice versa. In die literatuur van beide Carrera et al. en Piefort word Eerste Orde Skuifvervormings Teorie (EOST) gebruik in eindige element analises om die strukturele en elektriese gedrag van ’n plaat of dop te karakteriseer. EOST, ook bekend as Mindlin-Reissner teorie, is ’n plaat buigings-teorie wat ’n dwarsvervormingverspreiding aanneem deur die dikte van die plaat. Hierdie teorie word gesien as ’n verbetering op die standaard teorieë soos bv. Kircho of Timoshenko se teorieë. Daar bestaan baie optimeringstegnieke wat geklassifiseer word as ’direkte soek’ of ’hellinggebaseerde’ metodes. Partikel swerm-optimering (PSO) is ’n direkte soekmetode. Dit boots die gedrag van ’n swerm voëls of ’n skool visse in hulle poging om kos te vind, na. PSO se wiskundige stelling karakteriseer ’n aanvanklike stel onbekende partikels binne ’n afgebakende soekgebied wat vergelyk word met ’n stel van die beste plaaslike partikels sowel as ’n enkele beste globale partikel. Die vergelykings word gebruik om die swerm met elke siklus op te dateer. Regressie is ’n metode waarin toetsdata gebruik word om ’n benaderde funksie te konstrueer wat ongeveer voorspel hoe die regte funksie lyk. Die doel van hierdie werk is om die piezoelektriese saamgestelde laag te optimeer en die interaksie van die totale gedrag van die struktuur te verbeter. Uitgebreide modellering word uitgevoer en getoets met eweknie-beoordeelde literatuur om die akkuraatheid en korrektheid te bewys.

The electrical and optical properties of boron doped hydrogenated amorphous silicon thin films (a-Si) were investigated to determine the effect of boron and hydrogen incorporation on carrier transport. The a-Si thin films were grown by plasma enhanced chemical vapor deposition (PECVD) at various boron concentrations, hydrogen dilutions, and at differing growth temperatures. The temperature dependent conductivity generally follows the hopping conduction model. Above a critical temperature, the dominant conduction mechanism is Mott variable range hopping conductivity (M-VRH), where p = ¼, and the carrier hopping depends on energy. However, at lower temperatures, the coulomb interaction between charge carriers becomes important and Efros-Shklosvkii variable hopping (ES-VRH) conduction, where p=1/2, must be included to describe the total conductivity. To correlate changes in electrical conductivity to changes in the local crystalline order, the transverse optical (TO) and transverse acoustic (TA) modes of the Raman spectra were studied to relate changes in short- and mid-range order to the effects of growth temperature, boron, and hydrogen incorporation. With an increase of hydrogen and/or growth temperature, both short and mid-range order improve, whereas the addition of boron results in the degradation of short range order. It is seen that there is a direct correlation between the electrical conductivity and changes in the short and mid-range order resulting from the passivation of defects by hydrogen and the creation of trap states by boron. This work was done under the ARO grant W911NF-10-1-0410, William W. Clark Program Manager. The samples were provided by L-3 Communications.

Functional materials, particularly metal oxides, have been the focus of much attention in solid state chemistry for many years and impact every aspect of modern life. The approach adopted in this thesis to access desirable functionality for enhanced fundamental understanding is via modifying existing materials by deploying reducing synthetic procedures. This work spans several groups of inorganic crystalline materials, but is unified by the development of new properties within host compounds of particular relevance to solid oxide fuel cell technology, which allow interstitial oxide ion conduction at elevated temperatures. The Ca₁₂Al₁₄O₃₂e₂ electride was successfully synthesized by replacing the mobile extra-framework oxygen ions with electrons acting as anions. The high concentration of electrons in the C12A7 electride gives rise to an exceptionally high electronic conductivity of up to 245 S cm⁻¹ at room temperature. Making use of the high density of electrons in Ca₁₂Al₁₄O₃₂e₂ electride, the strong N-N bonds in N₂ was found to be broken when heating Ca₁₂Al₁₄O₃₂e₂ in a N₂ atmosphere. A reaction between silicate apatites and the titanium metal yielded another completely new electride material La₉.₀Sr₁.₀(SiO₄)₆O₂.₄e₀.₂ which was found to be a semiconductor. To fully understand the role of oxygen interstitials in silicate apatites, high-resolution transmission electron microscopy (HRTEM) was employed as the main technique in probing how the oxygen nonstoichiometry is accommodated at the atomic level. Atomic-resolution imaging of interstitial oxygen in La₉.₀Sr₁.₀(SiO₄)₆O₂.₅ proved to be a success in this thesis. Substitution of oxygen in 2a and interstitial sites with fluoride ions in La[subscript(8+y)]Sr[subscript(2- z)](SiO₄)₆O[subscript(2+(3y-2z)/2)] (0<y<2, 0<z<2) could be an approach to enriching the functionalities in the apatite structure. A wide range of fluoride substitution levels was tolerated in La[subscript(10-x)]Sr[subscript(x)](SiO₄)₆O[subscript(3-1.5x)]F[subscript(2x)] (x= 0.67, 1, 1.5, 2) and AC impedance measurements were found in support of a tentative conclusion that fluoride ions could be mobile in fluorinated apatites. The last part of this thesis was focused on a new class of fast oxide ion conductors based on Ge₅P₆O₂₅ whose performance was superior to both La₉.₀Sr₁.₀(SiO₄)₆O₂.₅ and Ca₁₂Al₁₄O₃₃ in the low temperature range.

Materiais da família ACu3Ti4O12 (ACTO) são potenciais candidatos para aplicação como dielétricos em capacitores cerâmicos devido aos seus altíssimos valores de constante dielétrica (&epsilon;\'), podendo chegar a 105 à temperatura ambiente. Entretanto, a origem deste fenômeno, denominado constante dielétrica gigante (CDG), é ainda uma questão altamente discutida na literatura. Deste modo, para compreender melhor os mecanismos por trás da manifestação desta CDG, neste trabalho os compostos ACu3Ti4O12 (com A = Ca, Bi2/3) foram sintetizados por uma rota baseada no método dos precursores poliméricos, sendo as reações envolvidas durante a síntese investigadas por análise térmica diferencial (ATD) e termogravimentria (TG). O subsequente processamento cerâmico foi realizado via sinterização tanto convencional quanto não convencional, utilizando, neste último caso, sinterização a laser e assistida por campo elétrico. As características (micro)estruturais foram avaliadas por meio de difratometria de raios X (DRX), microscopia eletrônica de varredura (MEV) e espectroscopia de energia dispersiva de raios X (EDX). Já as propriedades (di)elétricas foram estudadas, em nível microestrutural, utilizando espectroscopia de impedância (EI). Destas caracterizações, verificou-se que tanto as características (micro)estruturais quanto as propriedades (di)elétricas são fortemente influenciadas pelas condições de processamento. Neste sentido, mostramos que estes materiais podem apresentar baixos valores de permissividade à temperatura ambiente (&epsilon;\' ~ 102), típicos da resposta do volume, quando possuem grãos resistivos. Em contrapartida, quando as cerâmicas apresentam grãos semicondutores, valores de constante dielétrica gigante (&epsilon;\' >103) são verificados à temperatura ambiente devido à manifestação de efeitos de polarização interfacial. O caráter semicondutor dos grãos surge de maneira termicamente assistida. Isto ocorre porque, em maiores temperaturas, há uma migração de Cu para as regiões intergranulares das cerâmicas e também uma reação de redução do Cu2+ em Cu+. Durante o resfriamento o Cu+ reoxida, dando origem a semicondutividade dos grãos (deficientes em Cu). Como as condições empregadas na sinterização influenciaram as propriedades finais das cerâmicas, incluindo tamanho médio de grãos, decidimos inovar no processamento cerâmico ao aplicar um campo elétrico durante o tratamento térmico partindo de um pó ainda amorfo. Isto levou à observação de dois cenários: i) em altos campos, o pó sai de seu estado amorfo, passa pela cristalização de fases intermediárias, seguida de síntese ultrarrápida (flash synthesis), sem densificação; ii) em baixos campos, o pó transita do estado amorfo à fase final (passando pela cristalização das fases intermediárias), acompanhada de sinterização ultrarrápida (flash sintering), com alta densificação, tudo isso em um único experimento (FAST O3S). Finalmente, mostramos assim que utilizar um campo elétrico durante o tratamento térmico pode acelerar significativamente as taxas tanto de síntese quanto de sinterização, o que abre um novo paradigma no processamento de materiais cerâmicos. / Materials of the ACu3Ti4O12 (ACTO) family are potential candidates for application as dielectric in ceramic capacitors due to their extremely large dielectric constant (&epsilon;\'), which can reach 105 at room temperature. However, the origin of such large &epsilon;\' values, known as giant dielectric constant (GDC), is still an open debate in the literature. In order to better understand the mechanisms behind the manifestation of the GDG phenomenon, in this work, the compounds ACu3Ti4O12 (with A = Ca, Bi2/3) were synthesized by applying a modified polymeric precursor method. The reactions taking place during the powders synthesis were investigated through differential thermal analysis (DTA) and thermogravimetry (TG). The ceramic processing was then performed via conventional as well as non-conventional sintering, using, in the latter case, both laser and electric field-assisted sintering. The (micro)structural characteristics were evaluated by X-ray diffraction (DRX), scanning electron microscopy (SEM), and energy dispersive X-ray spectroscopy (EDX). Regarding the (di)electric properties, they were examined (at the microstructural level) using impedance spectroscopy (IS). We have shown from these characterizations that both (micro)structural and (di)electric features are strongly dependent on processing conditions. In this sense, we have demonstrated that these materials might present a low permittivity at room temperature (&epsilon;\' ~ 102), typical from the bulk response, when the ceramic grains are resistive. On the other hand, when the grains are semiconducting, giant dielectric constant values (&epsilon;\' >103) are verified at room temperature due to the manifestation of interfacial polarization effects. The semiconducting nature of the grains is promoted by a thermally-assisted mechanism, i.e., at higher temperatures there is Cu migration towards the ceramic intergranular areas and also a reduction of Cu2+ to Cu+. During cooling, the Cu+ re-oxidizes yielding the grain (Cu-deficient) semiconductivity. Since the conditions employed during the sintering have influenced the final ceramic properties, including the average grain size, we propose a novel approach to the ceramic processing by applying an electric field during the heat treatment starting from an amorphous powder, which led to the following scenarios: i) powder crystallization into the intermediate phases and then instantaneously into the final phase (flash synthesis), displaying no densification, at high fields; ii) powder transition from amorphous to the final phase (through crystallization into intermediate phases), followed by sintering with high densification, at low fields: this is the fast one-step synthesis plus sintering (FAST O3S) of materials, which ends with the so-called flash sintering. Finally, we have demonstrated that both synthesis and sintering rates can be enhanced by applying an electric field during the heat treatment, opening a new paradigm for ceramic processing.

Pour étendre l'utilisation des composites dans des applications plus variées (applications intelligentes et multifonctionnelles), l'une des barrières est leur faible conductivité électrique et thermique. Dans le cas de composites renforcés par des fibres de carbone, la matrice organique est responsable des propriétés isolantes du composite résultant. L'une des solutions pour améliorer les conductivités des matériaux est l'utilisation des nanocharges conductrices. L'amélioration des propriétés électriques et thermiques des polymères nanochargés est une problématique récurrente dans la littérature. Cependant, étudier les propriétés des composites à fibre de carbone continue et nanochargés est moins abordée. Ce travail porte sur la fabrication et la caractérisation des composites nanochargés par du noir de carbone et des nanotubes de carbone. Tout d'abord, un intérêt particulier a été accordé à la phase délicate de la fabrication. Comme mentionné ci-dessus, la mise en œuvre des composites à renfort continu et matrice nanochargée implique des problèmes liés à l'agglomération et à la dispersion inhomogène des nanocharges dans le composite final. Pour résoudre ces problèmes, le choix de la matrice thermoplastique (Polyamide 6) était judicieux. En fait, la dispersion des nanocharges a été faite par extrusion bi-vis qui est connue comme l'une des voies les plus efficaces de séparation d'agglomérats. De plus, la méthode de fabrication à base de films de Polyamide 6, appelée film stacking, assure une partition homogène dès le début du processus. Des observations MEB ont été effectuées pour localiser les nanoparticules. Ceux-là ont montré que les particules pénétraient dans la zone des fibres. En effet, en atteignant le cœur des torons, les nano-charges ont créé un réseau de connectivité entre les fibres pour le passage de courant. Ceci explique l'amélioration constatée de la conductivité électrique des composites en présence de noir de carbone et des nanotubes de carbone. Ces essais ont été réalisés avec la méthode à 4 points. La conductivité électrique du composite à matrice « pure » est passée de 20S / cm à 80S / cm en ajoutant 8% en poids de noir de carbone et à 15S / cm en ajoutant 18% en poids de la même charge nanométrique. Pour les nanotubes de carbone, avec 2,5% en poids, la conductivité était d'environ 150S / cm. Pour les propriétés thermiques, des tests basés sur l'effet Joule ont été réalisés. L'augmentation de la température a été enregistrée en utilisant une caméra IR. Les résultats obtenus sont en accord avec ceux de la conductivité électrique, montrant une amélioration du comportement thermique en présence de nanocharges. Grâce à ces résultats, l'utilisation de ces composites comme outil de suivi d’endommagement était possible. Par ailleurs, la méthode de variation de la résistance électrique a été effectuée. Les matériaux nanochargés ont montré une meilleure sensibilité aux endommagements. Les résultats ont été comparés aux outils classiques de suivi d’endommagement. A la fin, plusieurs applications « intelligentes » ont été testées telles que : le composite à gradients de propriétés et des matériaux nanochargés cousus. / To extend the use of composites in more varied application (smart applications, multifunctional issues), one of the actual barrier is their poor electrical and thermal conductivities. In the case of carbon fiber reinforced composites, organic matrix are in charge of the insulating properties of the resulting composite. One of the solutions to enhance conductivities of materials is the use of conductive nanofillers. Improving the electrical and thermal properties of nanofilled polymers has been investigated in several studies. However, studiing the properties of continuous carbon fiber nano-filled composites is less approached. This work tends to fabricate and characterize carbon black and carbon nanotubes nano-filled composites. First of all, special interest was given to the delicate phase of manufacturing. As mentioned before, processing continuous fiber reinforced nanofilled polymers implies issues related to nanofillers agglomeration and inhomogeneous dispersion in the final composite. To resolve these problems, the choice of the thermoplastic (Polyamide6) matrix seemed preferable. In fact, the dispersion of nanofillers was made by twin screw extrusion which is known as one of the most effective agglomeration separation ways. Adding to this, the fabrication method based on Polyamide 6 shects called film stacking, ensure a homogeneous partition at the beginning of the process. SEM observations were performed to localize the nano-particles. It showed that particles penetrated on the fiber zone. In fact, by reaching the fiber zone, the nano-fillers created network connectivity between fibers which means an easy pathway for the current. It explains the noticed improvement of the electrical conductivity of the composites by adding carbon black and carbon nanotube. This test was performed with the 4 points electrical circuit. It shows that electrical conductivity of 'neat' matrix composite passed from 20S/cm to 80S/cm by adding 8wt% of carbon black and to 15S/cm by adding 18wt% of the same nano-filler. For carbon nanotubes, with '2.5wt% the conductivity was around 150S/cm. For the thermal properties, tests based on Joule's effect were performed. The rise of temperature was recorded using IR camera. Results obtained are in agreement with the electrical conductivity ones, showing enhancement of the thermal behavior in presence of nanofillers. Thanks to these results, the use of these composites as a damage-monitoring tool was possible. By the way, the electrical resistance change method was performed. Nanofilled materials showed better sensitivity to damage. Results were compared with classical damage monitoring tools. At the end, several 'smart' applications were tested such as graded functionalities composite and stitched nanofilled materials.

L'objectif principal de ce travail est l'étude de la résistance au lavage des connections faites par fils électriques développées pour la réalisation de textiles intelligents. Cette étude est basée sur l'utilisation de trois différents fils électriques par la technique de broderie ; deux différents fils métalliques (M-1& M-2) et un fil enduit par de l'argent (S.C). Les échantillons ont été préparés en utilisant une machine industrielle de broderie et en utilisant un point de type 300, plus précisément un point 302 (zigzag) en faisant varié l'intervalle entre deux points successifs (1,2 et 3rnm). Ces échantillons devant pouvoir s'intégrer au sein d'un vêtement, leur« confectionnabilité »a été testés au travers des tests KES (Kawabata Evaluation System) en se concentrant sur les propriétés de flexion et de cisaillement de l'étoffe ainsi « instrumenté » conformément aux recommandations trouvées dans la littérature. Cette étude a été menée sur les échantillons initiaux mais aussi sur les échantillons ayant subis 1, 5 et 10 lavages. En parallèle avec ces caractérisations mécaniques, une étude électrique de ces derniers a été entreprise. Ont été testées, l'impédance de la connexion et aussi sa réponse en fréquence (de 100Hz à 11Mhz). L'analyse des résultats a mis en évidence un comportement en transmission du signal de type «second ordre », avec une évolution de la fréquence propre du filtre ainsi constitué vers les fréquences plus basses. Tous les échantillons ont ensuite été soumis à un lavage. Ces tests ont été répétés après chaque lavage jusqu'au 10ème. A partir des résultats obtenus nous avons pu établir un modèle de comportement et mettre en évidence une complexification du réseau de connexion surtout dans le cas des fils métalliques utilisés. Toutes ces expériences et modèles proposés, nous ont permis de conclure quant au potentiel important de ces types de technique de connexion et de proposer une série d'extension de ces travaux dans le cadre de travaux futur. / Main objective of this work is to study the washing behavior of textile based connections developed by using conductive threads. Two metallic threads (M-l & M-2) and one silver coated thread (S.C) have been used to make samples. The samples have been fabricated with different numbers of stitches per cm by using these conductive threads. After several tests it has been concluded to use the metallic thread in the bobbin of Jock stitch machine or embroidery machine. Embroidery machine has been used to make the samples. The embroidery has been done with zigzag stitch and samples were made. Three different distances between two consecutive stitches have been used that are 1mm, 2mm and 3mm. Samples have been characterized for mechanical (shear & bending) properties, using a KAWABATA testing instrument. Considerable differences have been observed among three types of threads. Graphical representation made it easy to highlight the behavioural aspects of each type. Then at other series of samples have been produced having different stitch densities. These samples then analyzed for electric properties by using mulitmeter, teraohm meter. Samples were also analyzed for signal transmission properties with the help of a frequency generator and an oscilloscope. The attenuation and phase angles were calculated at different frequencies ranging from 100Hz to 11MHz. Very interesting behaviour of the circuits have been observed and discussed in detail. AIL the samples are then subjected to washing and were again tested for all properties (shearing, bending, electric, and signal transmission).The tests have been repeated after each wash and observed the changes. In the final part of thesis all the results have been discussed, reasons have been identified and conclusion has been made.

This thesis discusses the investigation and utilization of a new promising thin-film material, liquid crystal polymer (LCP), for microwave and millimeter-wave (mm-wave [>30 GHz]) components and packages. The contribution of this research is in the determination of LCP's electrical and mechanical properties as they pertain to use in radio frequency (RF) systems up to mm-wave frequencies, and in evaluating LCP as a low-cost substrate and packaging material alternative to the hermetic materials traditionally desired for microwave circuits at frequencies above a few gigahertz (GHz). A study of LCP's mm-wave material properties was performed. Resonant circuit structures were designed to find the dielectric constant and loss tangent from 2-110 GHz under both ambient and elevated temperature conditions. Several unique processes were developed for the realization of novel multilayer LCP-based RF circuits. These processes include thermocompression bonding with tight temperature control (within a few degrees Celsius), precise multilayer alignment and patterning, and LCP laser processing with three different types of lasers. A proof-of-concept design that resulted from this research was a dual-frequency dual-polarization antenna array operating at 14 and 35 GHz. Device characterization such as mechanical flexibility testing of antennas and seal testing of packages were also performed. A low-loss interconnect was developed for laser-machined system-level thin-film LCP packages. These packages were designed for and measured with both RF micro-electromechanical (MEM) switches and monolithic microwave integrated circuits (MMICs). These research findings have shown LCP to be a material with uniquely attractive properties/capabilities for vertically integrated, compact multilayer LCP circuits and modules.

The absence of long-range order in glassy chalcogenides provides the convenience of changing the elemental ratios and hence the properties over a wide range. The interesting properties exhibited by chalcogenide glasses make them suitable materials for Phase Change Memories (PCM) and other applications such as infrared optical devices, photo-receptors, sensors, waveguides, etc. One of the most remarkable properties of chalcogenides is their electrical switching behavior. Reversible (threshold type) or irreversible (memory type) switching from a high resistance OFF state to a low resistance ON state in glassy chalcogenides occurs at a critical voltage called the threshold/switching voltage (VT). Investigations on the switching behavior and its composition dependence throw light on the local structural effects of amorphous chalcogenide semiconductors and also help us in identifying suitable samples for PCM applications. Thermal analysis by Differential Scanning Calorimetry (DSC) has been extensively used in glass science, particularly for measurements of thermal parameters such as enthalpy of relaxation, specific heat change, etc., near glass transition. Quite recently, the conventional DSC has been sophisticated by employing a composite temperature profile for heating, resulting in the Temperature Modulated DSC (TMDSC) or Alternating DSC (ADSC). Measurements made using ADSC reveal thermal details with enhanced accuracy and resolution, and this has lead to a better understanding of the nature of glass transition. The thermal parameters obtained using DSC/ADSC are also vital for understanding the electrical switching behavior of glassy chalcogenides. The motivation of this thesis was twofold: The first was to develop a novel, high voltage programmable power supply for electrical switching analysis of samples exhibiting high VT, and second to investigate the thermal and electrical switching behavior of certain Se-Te based glasses with Ge and Sb additives. The thesis contains seven chapters: Chapter 1: This chapter provides an overview of amorphous semiconductors (a-SC) with an emphasis on preparation and properties of glassy chalcogenides. The various structural models and topological thresholds of a-SC are discussed with relations to the glass forming ability of materials. The electronic band models and defect states are also dealt with. The essentials of electrical switching behavior of chalcogenides are discussed suggesting the electronic nature of switching and the role of thermal properties on switching. Chapter 2: The second chapter essentially deals with theory and practice of the experimental techniques adopted in the thesis work. The details of the melt-quenching method of synthesizing glassy samples are provided. Considering the importance, the theory of thermal analysis by DSC & ADSC, are discussed in detail, highlighting the advantages of the latter method adopted in the thesis work. The instrumentation and electronics, developed and used for electrical switching analysis are also introduced at a block diagram level. Finally, the methods used for structural analysis are briefed. Chapter 3: This chapter is dedicated to the design and development details of the programmable High Voltage dc Power Supply (HVPS: 1750 V, 45 mA) undertaken in the thesis work. The guidelines used for power supply topology selection, the specifications and block diagram of the HVPS are provided in that sequence. The operation of the HVPS is discussed using the circuit diagram approach. The details of software control are also given. The performance validations of the HVPS, undertaken through voltage & current regulation tests, step & frequency response tests are discussed. Finally, the sample-test results on the electrical switching behavior of representative Al20As16Te64 and Ge25Te65Se10 samples, obtained using both the current & voltage sweep options of the HVPS developed are illustrated. Chapter 4: Results of the thermally induced transitions governed by structural changes which are driven by network connectivity in the GexSe35-xTe65 (17 ≤ x ≤ 25) glasses, as revealed by ADSC experiments, are discussed in this chapter. It is found that the GexSe35-xTe65 glasses with x ≤ 20 exhibit two crystallization exotherms (Tc1 & Tc2), whereas those with x ≥ 20.5, show a single crystallization reaction upon heating (Tc). The glass transition temperature of GexSe35-xTe65 glasses is found to show a linear, but not-steep increase, indicating a progressive and not an appreciable build-up in network connectivity with Ge addition. The exothermic reaction at Tc1 has been found to correspond to the partial crystallization of the glass into hexagonal Te and the reaction at Tc2 is associated with the additional crystallization of rhombohedral Ge-Te phase. It is also found that the first crystallization temperature Tc1 of GexSe35-xTe65 glasses of lower Ge concentrations (with x ≤ 20), increases progressively with Ge content and eventually merges with Tc2 at x = 20.5 (<r> = 2.41); this behavior has been understood on the basis of the reduction in Te-Te bonds of lower energy and an increase in Ge-Te bonds of higher energy, with increasing Ge content. Chapter 5: This chapter deals with the electrical switching studies on GexSe35-xTe65 (17 ≤ x ≤ 25) glasses, with an emphasis on the role of network connectivity/rigidity on the switching behavior. It is found that the switching voltage (VT) increases with Ge content, exhibiting a sudden jump at x=20, the Rigidity Percolation Threshold (RPT) of the system. In addition, the switching behavior changes from memory to threshold type at the RPT and the threshold switching is found to be repetitive for more than 1500 cycles. Chapter 6: In this chapter, the results of thermal analysis (by ADSC) and electrical switching investigations on SbxSe55-xTe45 (2 ≤ x ≤ 9) are discussed. It is found that the addition of trivalent Sb contributes very meagerly to network growth but directly affects the structural relaxation effects at Tg. Further, SbxSe55-xTe45 glasses exhibit memory type electrical switching, which is understood on the basis of poor thermal stability of the samples. The metallicity factor is observed to outweigh the network factor in the composition dependence of VT of SbxSe55-xTe45 glasses. Chapter 7: The chapter 7 summarizes the results obtained in the thesis work and provides the scope for future work. The references are cited in the text along with the first author’s name and year of publication, and are listed at the end of each chapter in alphabetical order.

[Truncated abstract] Over the past decade, the group III-nitride semiconducting compounds (GaN, AlN, InN, and their alloys) have attracted tremendous research efforts due to their unique electronic and optical properties. Their low thermal carrier generation rates and large breakdown fields make them attractive for the development of robust electronic devices capable of reliable operation in extreme conditions, i.e. at high power/voltage levels, high temperatures and in radiation environments. For device applications in radiation environments, such as space electronics, GaN-based devices are expected to manifest superior radiation hardness and reliability without the need for cumber- some and expensive cooling systems and/or radiation shielding. The principle aim of this Thesis is to ascertain the level of susceptibility of current GaN-based elec- tron devices to radiation-induced degradation, by undertaking a detailed study of 60Co gamma-irradiation-induced defects and defect-related effects on the electrical characteristics of n-type GaN-based materials and devices . . . While the irradiation-induced effects on device threshold voltage could be regarded as relatively benign (taking into account that the irradiation levels employed in this study are equivalent to more than 60 years exposure at the average ionising dose rate levels present in space missions), the observed device instabilities and the degradation of gate current characteristics are deleterious effects which will have a significant impact on the performance of AlGaN/GaN HEMTs operating in radiation environments at low temperatures, a combination of conditions which are found in spaceborne electronic systems.

Τα Νανοσύνθετα συστήματα πολυμερικής μήτρας – σιδηροηλεκτρικών ή πιεζοηλεκτρικών σωματιδίων (κεραμικά εγκλείσματα) αναμένεται να αποτελέσουν μια νέα γενιά υψηλού τεχνολογικού ενδιαφέροντος που θα επιδεικνύουν λειτουργικές ιδιότητες λόγω της ποικίλης πόλωσης των κεραμικών νανοσωματιδίων. Η διασπορά κεραμικών εγκλεισμάτων στο εσωτερικό πολυμερικής μήτρας προσδίδει στα σύνθετα συστήματα βελτιωμένη μηχανική και ηλεκτρική συμπεριφορά. Τέτοιου τύπου συστήματα υλικών, που έχουν υψηλή ηλεκτρική διαπερατότητα (high-Κ materials) χρησιμοποιούνται σε ηλεκτρονικές εφαρμογές, καθώς μειώνουν τα ρεύματα διαρροής και παράλληλα λειτουργούν ως ενσωματωμένοι νανο-πυκνωτές και αισθητήρες ακουστικών εκπομπών. Η ηλεκτρική απόκριση τους, εκφράζεται κυρίως μέσω της ηλεκτρικής διαπερατότητας και μπορεί να ρυθμιστεί, ελέγχοντας τον τύπο, το μέγεθος και την ποσότητα της κεραμικής ενίσχυσης. Η ενσωμάτωση σιδηροηλεκτρικών ή πιεζοηλεκτρικών κρυστάλλων, που επιδεικνύουν υψηλή πόλωση, σε μια πολυμερική μήτρα, όπως η εποξειδική ρητίνη – που εν γένει είναι ηλεκτρικός μονωτής- με χαμηλή ηλεκτρική διαπερατότητα και υψηλή διηλεκτρική αντοχή μπορεί να οδηγήσει στην ανάπτυξη ενός ευφυούς συστήματος. Σκοπός αυτής της εργασίας είναι η παρασκευή και ο χαρακτηρισμός σύνθετων πολυμερικών συστημάτων εποξειδικής ρητίνης – νανοσωματιδίων τιτανικού ψευδάργυρου (ZnTiO3) καθώς και σύνθετων υβριδικών συστημάτων εποξειδικής ρητίνης - νανοσωματιδίων τιτανικού ψευδάργυρου (ZnTiO3) και τιτανικού βαρίου (BaTiO3) ώστε να οδηγηθούμε σε ένα σύστημα υλικών με βέλτιστη συμπεριφορά. Στο θεωρητικό κομμάτι αυτής της εργασίας συζητούνται βασικές έννοιες και θεωρίες που αφορούν τα σύνθετα υλικά, τη θεωρία των διηλεκτρικών και ενεργών διηλεκτρικών, την ηλεκτρική συμπεριφορά σύνθετων υλικών με πολυμερική μήτρα καθώς και πειραματικές τεχνικές χαρακτηρισμού. Στο πειραματικό μέρος, νανοσύνθετα πολυμερικά συστήματα παρασκευάστηκαν από εποξειδική ρητίνη και νανοσωματίδια ZnTiO3 και BaTiO3. Η μέση διάμετρος σωματιδίων βάσει των προδιαγραφών του προμηθευτή ήταν λιγότερο από 100nm για το ZnTiO3 και στην περιοχή των 30 - 50nm για το BaTiO3. Στη συνέχεια τα νανοσύνθετα υποβλήθηκαν σε μορφολογικό, θερμικό και ηλεκτρικό χαρακτηρισμό. Η μορφολογία των δειγμάτων εξετάστηκε για τυχούσα παρουσία κενών (voids) και συσσωματωμάτων (clusters) μέσω του Ηλεκτρονικού Μικροσκοπίου Σάρωσης (SEM) και η θερμική τους απόκριση μέσω της Διαφορικής Θερμιδομετρίας Σάρωσης (DSC). Η διασπορά των κεραμικών εγκλεισμάτων θεωρήθηκε ικανοποιητική, παρόλο που συνυπάρχουν οι νανοδιασπορές με συσσωματώματα. Οι διηλεκτρικές ιδιότητες και τα σχετιζόμενα φαινόμενα διεργασιών χαλάρωσης μελετήθηκαν με χρήση της Διηλεκτρικής Φασματοσκοπίας Ευρέως Φάσματος (BDS) στο εύρος θερμοκρασιών -100 oC έως 160 oC και στο διάστημα συχνοτήτων 10-1 Hz έως 106 Hz. Η ανάλυση των πειραματικών αποτελεσμάτων διεξήχθη με τη χρήση των φορμαλισμών της ηλεκτρικής διαπερατότητας και του ηλεκτρικού μέτρου. Από τα πειραματικά αποτελέσματα προκύπτει πως παρατηρούνται διηλεκτρικές χαλαρώσεις που οφείλονται τόσο στην πολυμερική μήτρα, όσο και στην ενισχυτική φάση. Τα φάσματα των υβριδικών συστημάτων καταγράφουν τουλάχιστον τέσσερεις διακριτούς τρόπους χαλάρωσης. Αυτά αποδίδονται στη διεπιφανειακή πόλωση (Interfacial Polarization ή φαινόμενο MWS) μήτρας/εγκλεισμάτων, στην α- χαλάρωση λόγω υαλώδους μετάβασης του πολυμερούς και στην β- και γ- χαλάρωση εξαιτίας της κίνησης πλευρικών πολικών ομάδων και τοπικής κίνησης μικρών τμημάτων της πολυμερικής αλυσίδας. Η λειτουργικότητα των νανοσύνθετων σχετίζεται με την μεταβολή της πόλωσης, που σχετίζεται ευθέως με το πραγματικό μέρος της ηλεκτρικής διαπερατότητας, την εξάρτηση της ειδικής αγωγιμότητας από την θερμοκρασία και την περιεκτικότητα σε ενισχυτικό μέσο και την δυνατότητα αποθήκευσης ενέργειας. / Nanocomposite systems, which include ferroelectric or piezoelectric particles represent a novel class of materials which are expected to exhibit functional properties because of the varying polarization of the ceramic particles. Dispersing ceramic inclusions within a polymer matrix, results in enhanced mechanical and electrical behavior. Such material systems exhibiting enhanced electrical response are used in electronic applications, for the reduction of leakage currents, as integrated nano- capacitors and as acoustic emission sensors. The electrical response of these composites, namely dielectric permittivity and conductivity can be tailored, by controlling the type, the size and the amount of ceramic inclusions. The ceramic filler could be ferroelectric and/or piezoelectric crystal particles. Their high level of polarization can be combined with a polymer host, like an epoxy resin – which is, in general, electrical insulator – with low dielectric permittivity and high dielectric breakdown strength. This combination could lead in the development of a smart materials’ system. The aims of this work are the preparation and characterization of epoxy resin nanocomposites with embedded zinc titanate (ZnTiO3) and nanoparticles and in tandem hybrid system of epoxy resin– zinc titanate (ZnTiO3) and barium titanate (BaTiO3) nanoparticles. In the first part of this work basic aspects concerning composite materials, dielectric theory, electrical behaviour and characterization techniques of polymer matrix composites are presented. In the experimental part of this study, nanocomposites were prepared by employing commercially available materials such as epoxy resin, ceramic ZnTiO3 and BaTiO3 nanopowder. The mean particle diameter, as indicated by the supplier, was less than 100nm for ZnTiO3 and 30-50nm for BaTiO3 particles. Furthermore, morphology, thermal and electrical response of the produced specimens was examined. The morphology of the specimens was checked for voids and clusters, by means of Scanning Electron Microscopy and the thermal response via Differential Scanning Calorimetry (DSC). Ceramic particles distribution is considered as satisfactory, although clusters co-exist with nanodispersions in all the examined systems. The dielectric properties and the related relaxation phenomena were studied by means of Broadband Dielectric Spectroscopy (BDS) in the temperature range from -100 oC to 160 oC and frequency range from 10-1 Hz to 10-6 Hz. Experimental data analysis was conducted by means of dielectric permittivity and electric modulus formalisms. Based on the conducted analysis, the recorded relaxation phenomena include contributions from both the polymeric matrix and the reinforcing phase. In the spectra of hybrid nanocomposites at least four relaxation processes can be detected. They were attributed to Interfacial Polarization phenomenon (MWS effect), α-mode due to glass/rubber transition of the polymer and β- , γ- modes resulting from the motion of polar side groups and local motion of small segments of the polymer chain. The functionality of the nanocomposite systems is related to the variation of polarization, which is directly connected to the real part of dielectric permittivity, the dependence of conductivity on the temperature and the filler content, and the energy storage efficiency expressed by the density of energy.