The research described in this dissertation mainly covers the development of novel technologies for co-crystallisation along with the discovering of plumbagin co-crystal and thermodynamic interrelationship between the co-crystal polymorphs. Co-crystallisation is a fast growing field in the area of crystal design and has shown potential advantages in the field of pharmaceutical. Currently, many research groups are working on the development of new technologies for the synthesis of pure and stoichiometrically controlled co-crystals. In present study, three novel technologies have been developed for co-crystallisation, which include microwave assisted co-crystallisation, spherical crystallisation and microwave assisted sub-critical water processing. The microwave assisted co-crystallisation is a slurry based technology where, effects of drug solubility and dielectric properties of the solvent were investigated using caffeine / maleic acid as a model co-crystal pair. The mechanism of co-crystallisation under microwave irradiation has been proposed. The co-crystals of plumbagin with improved solubility were obtained with the coformers such as hydroquinone, resorcinol and urea using microwave assisted co-crystallisation technique. The spherical crystallisation technology was developed for co-crystallisation of carbamazepine / saccharin co-crystal pair and demonstrated its application for polymorphic control and as a potential technique for the purification of desired crystal form through surface energetic based separation. The thermodynamic interrelationship between Form I and Form II of carbamazepine / saccharin co-crystal was studied using different thermodynamic tests. The results obtained suggest that the carbamazepine / saccharin co-crystal polymorphs are monotropic. Microwave assisted sub-critical water processing has been explored as a green technology for the synthesis of co-crystals. Carbamazepine / saccharin co-crystal pair has been used as a model pair and effects of processing variables on the resulting crystal form and degradation of an API have been studied.

Ground penetrating radar (GPR) technology has existed for many decades, but it has only been in the last 20 to 30 years that it has undergone great development for use in near surface ground investigations. The early 1980's saw the first major developments in the application of GPR for pavements (i.e. engineered structures designed to carry traffic loads), and it is now an established investigation technique, with generic information included in several national standard guidance documents. Analysis of GPR data can provide information on layer depths, material condition, moisture, voiding, reinforcement and location of other features. Assessing the condition of pavements, in order to plan subsequent maintenance, is essential to allow the efficient long-term functioning of the structure and GPR has enhanced and improved the range and certainty of information that can be obtained from pavement investigations. Despite the recent establishment of the technique in pavement investigation, the current situation is one in which GPR is used routinely for pavement projects in only a minority of countries, and the specialist nature of the technique and the sometimes variable results that are obtained can mean that there is both a lack of appreciation and a lack of awareness of the potential information that GPR can provide. The fact that GPR is still a developing technique, and that many aspects of its use are specialised in their nature, means that there are also several technical aspects of GPR pavement investigations which have not been fully researched, and knowledge of the response of GPR to some material conditions has not been fully established. The overall aim of this EngD research project was to provide improved pavement investigation capabilities by enhancing the methodologies and procedures used to obtain information from GPR. Several discrete research topics were addressed through various research methods including a literature review, fieldwork investigations, experimental laboratory investigations and a review of previously collected data. The findings of the research allowed conclusions and recommendations to be made regarding improved fieldwork methodologies, enhancing information and determining material condition from previously collected GPR data, assessing the effect of pavement temperature and moisture condition on GPR data and also on managing errors and uncertainty in GPR data. During the EngD project, a number of documents and presentations have been made to publicise the findings both within the EngD sponsoring company (Jacobs) and externally, and an in-house GPR capability has been established within Jacobs as a direct result of the EngD project.

O titanato de estrôncio (SrTiO3) possui estrutura cristalina do tipo perovsquita. Materiais com este tipo de estrutura são utilizados para diversas aplicações, tais como, sensores, atuadores, em células a combustível de óxido sólido, entre outros. Devido as suas interessantes propriedades físicas, o SrTiO3 vem sendo intensamente estudado, em especial com a introdução de dopantes. Portanto, neste trabalho foi investigada a influência de diferentes teores de Ca (1; 2,5 e 5% mol) e Pr (0,025; 0,050; 0,075 e 1% mol) na microestrutura e propriedades elétricas e dielétricas do SrTiO3, assim como o material sem aditivos (puro). Os resultados mostram que após a sinterização do SrTiO3 puro, a microestrutura consiste de grãos poligonais com tamanho médio micrométrico, além de texturas lisas e rugosas. A condutividade elétrica das amostras sintetizadas sinterizadas a 1450 e 1500ºC é máxima para 2 horas de patamar. Apenas as amostras de SrTiO3 contendo 1% em mol de Ca apresentam fase única. O tamanho médio de grãos das amostras contendo 1% em mol de Ca é 10,65 ± 0,28 µm e para teores acima deste valor ocorre crescimento significativo dos grãos. As medidas de condutividade elétrica mostraram que as amostras contendo a adição de 1% em mol de Ca possuem maior condutividade dos grãos em relação ao material puro. Para as amostras contendo teores de até 0,075% mol de Pr, pode-se observar alguns grãos lisos e outros rugosos e não há variação considerável do tamanho médio de grãos. As amostras contendo menor teor de Pr (0,025% mol) apresentam maior condutividade dos grãos e contornos de grãos. As amostras de SrTiO3 sintetizado sinterizadas a 1450ºC/10 h apresentaram permissividade elétrica colossal em temperatura ambiente em altas frequências. / Strontium titanate (SrTiO3) exhibits cubic perovskite type crystalline structure at room temperature. Polycrystalline ceramics with this structure are potential candidates for a number of applications including sensors, actuators and in solid oxide fuel cells. Several properties of SrTiO3 are strongly dependent on addition of both donors and acceptors additives. Then, there is a growing interest for studying its properties as a function of type and concentration of additives. In this study, the effects of Ca (1, 2.5 and 5 mol%) and Pr (0.025 to 1 mol%) additions on microstructure and electric and dielectric properties of SrTiO3 were investigated. The microstructure of pure SrTiO3 consists of polygonal grains with average grain size in the micrometer range, and the electric conductivity is maximized after sintering for 2 h at 1450 and 1500ºC. Specimens containing 1 mol% Ca are single phase and the average grain size is 10.65 ± 0.28 µm, but for higher additive contents grain growth is observed. The electric conductivity of SrTiO3 with 1 mol% Ca is higher than that of the pure ceramic. Specimens containing Pr do not show significant grain growth, and the higher conductivity of grains and grain boundaries was achieved with 0.025 mol% Pr. Pure SrTiO3 sintered at 1450ºC for 10 h shows colossal dielectric permittivity (> 1.000) at room temperature, in contrast to specimens prepared with commercial powder (dielectric permittivity = 300), at high frequencies.

A method was developed to access the interior of light-guiding structures in order to exploit the enhanced sensing potential of the highly confined electromagnetic field distributions, located within the core of a waveguide. The work presented in this thesis explores therefore the possibilities of optical waveguide spectroscopy utilising transparent mesoporous thin-film waveguides deposited on top of athin gold layer. These multi-layer assemblies are employed in a prism-coupling attenuated total internal reflection (ATR) configuration. The angular read-out of the reflected light intensity allows label-free detection schemes with high sensitivity to changes of the dielectric environment in the case of the presence of analyte molecules within the probing region. This optical waveguide spectroscopy technique has been used to study the real-timediffusion of Ruthenium 535-bisTBA (N-719) dye into mesoporous nanocrystalline titaniumdioxide films. The porous films were prepared on top of gold substrates and prism coupling was used to create a guided wave in the nanocrystalline film. Dying was carried out by bring the film into contact with a 3 x 10-4 moldm-3 dye solution and using optical waveguide spectroscopy to monitor the change in both the refractive index and theextinction coefficient of the nanoporous layer as dye diffused into the porous network. Dyeuptake in a 1.27 μm film was slow with the refractive index of the film still increasing after 22 hours.

There is a growing interest in the field of Dielectric Elastomer Actuators (DEAs).A DEA consists of a thin DE lm coated with a compliant electrode. It expandsin planar directions and contracts in thickness under a driving voltage. Becauseof the similar actuation capability compared with human muscles, it is oftenreferred as artificial muscle. One possible application is to integrate the DEA inwearable devices for tremor suppression. In this thesis, the development of theDEA has been advanced towards this application in three aspects: performanceenhancement, modelling accuracy and self-sensing control. The results presented demonstrate that the combination of pre-strain and motion constraining enhances the force output of the DEA significantly but it also leads to the pre-mature electric breakdown that shortens the operational life. This drawback was suppressed by optimising the electrode configuration to avoid the electrically weak regions with low thickness across the DE lm, together with the lead contact o the active electrode region. The durability of the enhanced DEA was therefore improved significantly. Polyacrylate, a commonly used DE, was characterised for dynamic mechanical loading and electrical actuation. The conventional Kelvin-Voigt model was proved to be deficient in simulating the viscoelastic behaviour of polyacrylate in the frequency domain. The error in modelling was substantially reduced using a higher material model that contains multiple spring-damper combinations. It allows the system dynamics to be shaped over frequency ranges. A detailed procedure was given to guide the parameter identification in higher order material model. A novel self-sensing mechanism that does not require superposition of drivingvoltage and excitation signal was also designed. It reconfigures the conventionalDEA to have separate electrode regions for sensing and actuating. As the DElm deforms under driving voltage, the capacitive change in the electrode regionfor sensing was measured via a capacitor bridge and used as the feedback foractuation control. The self-sensing DEA can, therefore, be implemented with anyhigh voltage power supply. Moreover, the sensing performance is demonstratedto have improved consistency without interference of the electrical field. It alsohas a unique feature of DE lm wrinkling detection.

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.

Certos solos não saturados ao serem umedecidos experimentaram bruscas reduções de volume, sob cargas praticamente constantes. O fenômeno é atribuído a um colapso de estrutura do solo, donde a designação de solo colapsível. Essa redução de volume pode ocorrer sob a ação do próprio peso do solo, mas é mais comum ocorrer quando o solo está sujeito a um carregamento adicional. Muitos dos problemas de recalques nas áreas urbanas e industrias na Região Sudeste do Brasil estão associados ao colapso dos solos. Deformações induzidas por umedecimento (colapso) têm sido reportados como decorrrentes de vazamentos oriundo das redes de esgoto e de abastecimento de água. Porém, pouco se sabe sobre a influência de vazamentos de diferentes efluentes químicos nesse fenômeno e em outros fenômenos eventualmente associados com a dispersão dos solos. Neste trabalho, analisa-se o comportamento colapsível de dois solos típicos do interior do Estado de São Paulo, considerando diferentes soluções como líquido inundante. Utilizaram-se substâncias orgânicas e inorgânicas com o intuito de verificar a interferência de algumas propriedades químicas destas soluções (pH, constante dielétrica, concentração e temperatura) no comportamento colapsível dos solos. Para evitar a ação dos fluídos químicos na dispersão dos solos, realizou-se o \"pinhole test\". Análises porosimétricas por intrusão de mercúrio foram utilizadas para identificar mudanças ocorridas nos poros das amostras após os ensaios edométricos. Para a análise estrutural, foram analisadas lâminas delgadas em microscópio óptico. Verificou-se que a presença de um agente dispersivo na solução tende a influenciar o potencial de colapso dos solos. A constante dielétrica, o pH e a concentração mostraram-se influentes para alguns fluídos de saturação. Os resultados dos \"pinholes tests\" revelaram que o fluxo das diferentes soluções não provocou a dispersão do solo. Ensaios de porosimetria ) por intrusão de mercúrio indicaram que as deformações por colapso resultam de uma redução do volume de macroporos. A análise das lâminas delgadas mostrou diferentes facetas dos processos ocorrentes em nível estrutural, como diminuição considerável dos poros e modificações no plasma para as amostras inundadas com as soluções defloculantes de hexametafosfato de sódio e hidróxido de sódio. / Some non saturated soils show considerable volume reduction when wetted under constant loads. The phenomenon is attributed to soil structure collapse, thus the designation collapsible soils;. Volume reduction upon wetting can arise under soil self weight, but it is more common when the soil is subjected to an additional load. Many settlement problems in urban and industrial areas in Southern Brazil are associated to soil collapse. Wetting induced strains (collapse) have been related to water and sewer leakage. However little is known about the influence of different effluent leakage from industrial plants in the phenomenon and in other related phenomenon such as soil dispersion. This work deals with the collapsible behavior of two typical soils from the state of São Paulo assessed by means of wetting both soils with different chemical solutions. Organic and inorganic solutions were applied, aiming to verify the interference of some physic-chemical properties of the solutions (pH, dielectric constant, concentration, temperature) in the collapse behavior of the soils. The soil dispersion was evaluated through pinhole tests, where the same solutions used in the collapse tests were applied in the leaching procedures. Thin sections and mercury porosimetry of the soils were used to study the soil structural features. It is shown that the dielectric constant and the pH tends to influence the collapse potential of the soils when some solutions are concerned. Mercury intrusion tests have revealed that collapse deformations are related to macropores volume reduction. Thin sections have shown some features of the occurring processes on a structural levei, such as pore reductions and changes in fine matrix for the soil samples soaked with sodium hexametaphosphate and sodium hydroxide solution.

La production de nanoparticules (NPs) par des décharges spark en phase liquide permet d’atteindre des rendements jusqu’à présent inégalés de l’ordre de quelques centièmes de milligramme par joule. Même si l’essentiel de l’énergie est dissipé dans la formation de la décharge, l’érosion des électrodes métalliques permet la production efficace de NPs. La nature des NPs formées est largement tributaire du liquide diélectrique dans lequel la décharge est réalisée. Il est ainsi possible de contrôler les nanoparticules produites en choisissant de manière ad hoc les électrodes et le liquide. Nous cherchons dans ce travail à comprendre les mécanismes qui ont lieu durant la décharge en étudiant différents cas d’élaboration de NPs soit d’alliages soit de composites. Les NPs synthétisées auront des applications dans divers domaines selon le(s) matériau(x) choisi(s). À l’aide d’un générateur d’impulsions nanosecondes, les décharges ont été créées en appliquant une impulsion de haute tension (10 kV- 200ns- 10 Hz) entre deux électrodes immergées dans de l’azote liquide. Trois systèmes principaux ont été étudiés : Si-Sn, Cu-Zn et Cu-Ag. Les tests ont été réalisés avec des électrodes pures ou avec des alliages contenant les 2 éléments en proportions variables pour améliorer notre compréhension sur la manière dont les nanoparticules sont formées. Des analyses en microscopie électronique en transmission à haute résolution (HRTEM), en spectroscopie des rayons X à dispersion d'énergie (EDX), en spectroscopie de perte d'énergie des électrons (EELS) et des analyses de micro-diffraction ont été menées pour caractériser les NPs synthétisées (morphologie, cristallinité, composition chimique, etc.). Enfin, des mesures de spectroscopie d’émission optique résolues dans le temps ont été réalisées pour disposer d’informations sur l’évolution temporelle des raies émises au cours de la décharge et ainsi sur les conditions qui prévalent dans le plasma / Discharges in liquids offer a simple way to synthesize nanoparticles at high rate and low cost. When spark discharges are ignited in a dielectric liquid, a strong heating of the electrode material occurs, producing a metallic vapor from which nanoparticles grow by condensation. Even if most of the energy is dissipated in the formation of the discharge, the erosion of the metal electrodes allows the efficient production of NPs. The nature of the NPs formed is largely dependent on the dielectric liquid in which the discharge is performed. It is thus possible to control the nanoparticles produced by choosing the electrodes and the liquid in an appropriate manner. We seek in this work to understand the mechanisms that take place during the discharge by studying different cases of elaboration of NPs either alloys or composites. The synthesized NPs will have applications in various fields depending on the material(s) chosen. Using a nanosecond pulse generator, the discharges were created by applying a high voltage pulse (10 kV-200ns-10 Hz) between two electrodes immersed in liquid nitrogen. Three main systems have been studied: Si-Sn, Cu-Zn and Cu-Ag. The tests were performed with pure electrodes or alloys containing the 2 elements in varying proportions to improve our understanding of how nanoparticles are formed. High resolution transmission electron microscopy (HRTEM), energy dispersive X-ray spectroscopy (EDX), electron energy loss spectroscopy (EELS) and micro-diffraction analyzes were carried out to characterize the synthesized NPs (morphology, crystallinity, chemical composition, etc.). Finally, time-resolved optical emission spectroscopy measurements were performed to obtain information on the temporal evolution of the lines emitted during the discharge and thus on the conditions that prevail in the plasma

Metal oxide thin films serve as critical components in many modern technologies, including microelectronic devices. Industrial state-of-the-art production utilizes vapor-phase techniques to make high-quality (dense, smooth, uniform) thin film materials. However, vapor-phase techniques require large energy inputs and expensive equipment and precursors. Solution-phase routes to metal oxides have attracted great interest as cost-effective alternatives to vapor-phase methods and also offer the potential of large-area coverage, facile control of metal composition, and low-temperature processing. Solution deposition has previously been dominated by sol-gel routes, which utilize organic ligands, additives, and/or solvents. However, sol-gel films are often porous and contain residual carbon impurities, which can negatively impact device properties. All-inorganic aqueous routes produce dense, ultrasmooth films without carbon impurities, but the mechanisms involved in converting aqueous precursors to metal oxides are virtually unexplored. Understanding these mechanisms and the parameters that influence them is critical for widespread use of aqueous approaches to prepare microelectronic components. Additionally, understanding (and controlling) density and composition inhomogeneities is important for optimizing electronic properties. An overview of deposition approaches and the challenges facing aqueous routes are presented in Chapter I. A summary of thin film characterization techniques central to this work is given in Chapter II. This dissertation contributes to the field of solution-phase deposition by focusing on three areas. First, an all-inorganic aqueous route to high-κ metal oxide dielectrics is developed for two ternary systems. Chapters III and IV detail the film formation chemistry and film properties of lanthanum zirconium oxide (LZO) and zirconium aluminum oxide (ZAO), respectively. The functionality of these dielectrics as device components is also demonstrated. Second, the impact of steam annealing on the evolution of aqueous-derived films is reported. Chapter V demonstrates that steam annealing lowers processing temperatures by effectively reducing residual counterion content, improving film stability with respect to water absorption, and enhancing dielectric properties of LZO films. Third, density and composition inhomogeneities in aqueous-derived films are investigated. Chapters VI and VII examine density inhomogeneities in single- and multi-metal component thin films, respectively, and show that these density inhomogeneities are related to inhomogeneous metal component distributions. This dissertation includes previously published coauthored material.

This thesis presents an experimental study of the influence of an external field and alignment upon a colloid of a liquid crystal (octycyanobiphenyl denoted 8CB) and a silica gel of aerosil nano-particles. The first techniques used was an AC-calorimetry (alternating current heating) and the systems under investigation were firstly put under the influence of a magnetic field at John Hopkins University in Baltimore by professor Leheny's group. The experiments revealed changes in transition temperatures, nematic range and critical coefficient that could account for what we called a 'memory' of the above mentioned structures. The second technique, dielectric spectroscopy, was applied to the same very densities of mixture s mentioned in the first paragraph. The samples were applied in one procedure an increasingly higher alternating electric field. An overall increase of the capacitance of the sample was measured. The second experiment was to reproduce the application of the magnetic field from the AC-calorimetry experiment now with an electric field. In dielectric spectroscopy case, an increase in transition temperature after the application of the procedure was revealed.