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La thèse porte de manière générale sur les polymères électrostrictifs qui peuvent être utilisés soit comme actionneurs électromécaniques souples, soit comme capteurs ou récupérateurs d’énergie. Le premier chapitre est une introduction générale aux systèmes couplés électromécaniques. Le choix des matériaux est exposé et porte sur les élastomères diélectriques et les polyuréthanes (PU) chargés par des nanoparticules conductrices de noir de carbone (CB). Le second chapitre porte sur la réalisation des films. Des particules de CB sous forme de micelles préformées et une technique « solution-cast » sont employées dans cette optique. Ce procédé permet une bonne dispersion des charges. Une amélioration de la déformation d’un facteur 1,6 est obtenue par introduction de particules de CB à 0.89 vol%. Le troisième chapitre présente la modélisation de phénomènes comme la saturation de la polarisation qui implique directement une saturation de la déformation. En modélisant la polarisation comme une fonction non-linéaire dépendant de deux variables (la permittivité bas niveau et un champ de saturation), on décrit ainsi correctement plusieurs phénomènes qui ne peuvent être interprétés par une approche linéaire et homogène. Les simulations effectuées montrent une bonne corrélation avec les expérimentations menées. Le quatrième chapitre propose une comparaison entre les films PU purs et chargés. Cette analyse porte non seulement sur des mesures mécaniques et électriques mais également en XRD ou en DSC afin de détecter le niveau de cristallisation. Une dispersion importante a ainsi été observée visuellement. Des déformations de l’ordre de 50 % ont ainsi été obtenues. Le cinquième chapitre porte sur l’effet lié à l’injection de charges électriques par bombardement électronique (HEBI), sur la déformation électrostrictive. Une telle approche permet ainsi un gain d’un facteur de l’ordre de 2 sur la déformation et semble réduire les pertes de façon très conséquente. / In a general manner, the present thesis focuses on electrostrictive polymers which can be used either as flexible electromechanical actuators or as sensors or energy harvesters. Chapter 1 is a general introduction to electro-mechanical coupled systems. The choice of the materials is described and focuses on dielectric elastomers, polyurethane (PU) with conductive carbon black (CB) nano-particle fillers. Chapter 2 focuses on the film synthesis. CB nano-particles in the form of micelles and solution cast method were employed to provide good filler dispersion. The strain enhancement of a factor of 1.6 was obtained by 0.89 vol% CB doping. Chapter 3 exposes the modeling of electrostrictive actuation and in particular the saturation of the polarization. By modeling the polarization as a nonlinear function depending on two variables (low-level permittivity and saturation field), it is therefore possible to describe several phenomena that cannot be explained by a classical linear and homogeneous approach. Simulations performed using such an approach show a good agreement with experimental results. Chapter 4 presents the comparison between pure PU and composite films. It includes mechanical/electrical characterization as well as XRD or DSC measurements to detect the crystallization level. High dispersion level was visually confirmed. Strains of the order of 50 % were reached. Chapter 5 deals with the effect of electric charge injection by homogeneous electron beam irradiation (HEBI) on the electrostrictive strain. This technique therefore permits a gain of 2 on the obtained strain and seems to significantly reduce the losses in the material as well.

La thèse est consacrée aux matériaux électro-actifs, qui sont développés et conçus pour faire de la conversion entre énergie électrique et énergie mécanique. Avec les nouvelles technologies émergentes de transduction électromécanique, les polymères électro-actifs (EAP) ont gagné une attention considérable. Ils présentent de grandes déformations quand ils sont soumis à un champ électrique. Cependant, ces matériaux présentent de faibles permittivités et exigent pour fonctionner l’application de forts champs électriques. Les recherches entreprises dans la thèse traitent de différentes méthodes ayant pour but d'augmenter la permittivité des polymères et par conséquent d’améliorer les propriétés électromécaniques sous des champs électriques modérés. Les différentes approches consistent à la mise au point de nouveaux matériaux, par la méthode de mélange de polymères ou en utilisant un nouveau type de polymère, et par l'incorporation de nano-charges spéciales dans la matrice polymère. Un mélange de polyuréthane (PU) et PEMG obtenu à partir d'un procédé en solution conduit à des valeurs plus basses de module de Young, mais aussi à de plus faibles permittivités diélectriques. Il est cependant mis en évidence une amélioration des propriétés électromécaniques, par exemple, à le gain à des champs électriques modérés est d’un facteur 2, avec seulement 9% en poids de PEMG. Deux types de Pebax sont testés comme matrice polymère. Des valeurs très élevées de permittivités sont obtenus plus particulièrement pour le Pebax1657 mais liés pour ce matériau à des valeurs élevées de conductivité. En dépit de ces permittivités élevées, seule une légère amélioration de la conversion électromécanique est observée par rapport au polyurethane. Nous nous sommes également intéressés aux nanocomposites de polyuréthane basés sur desnanoparticules d'argent recouvertes de polymère polyvinylpyrrolidone (PVP). Un fin revêtement de polymère sur les nanoparticules d'argent conduit à une meilleure dispersion des charges dans les films de polyuréthane, et des valeurs plus élevées de permittivité. Différentes quantités d'Ag-PVP sont testées jusqu'au seuil de percolation proche de 45% en poids de charges. À partir des mesures par interférométrie laser et du nouveau dispositif de caractérisation croisée, les propriétés électromécaniques optimales sont obtenues pour 20% en poids de Ag-PVP, avecun gain de 2 à 6 par rapport au polyuréthane pur. Afin d'expliquer la différence entre les résultats expérimentaux et attendus, et par conséquent pour parvenir à une meilleure compréhension du comportement électromécanique de ces différents matériaux, certaines hypothèses ont été discutées et testées. Nous avons montré notamment une baisse des permittivités diélectriques sous champs électriques pour les Pebax et les nanocomposites, des problèmes d'absorption d'eau pour les Pebax et une diminution de cristallinité dans le cas des nanocomposites PU-Ag. / The thesis is devoted to electroactive materials, which are developed and designed to make conversion between the electricity and the mechanical form. With newer emerging electromechanical transduction technologies, electroactive polymers (EAP) have gained a considerable attention. The polymers are competitive in many applications such as actuators, sensors, robotic system and biological mimics since they are cheap, light, easy to process, and they present large electric field-induced strains. However, these materials suffer from the low permittivity and high voltage requirement to drive the actuations. The research undertaken for the thesis intends then to provide different methods in order to enhance the polymer permittivity and consequently the electromechanical activities at moderate electric fields. The different approaches consist on the development of new materials by polymer blend method or by using new kind of polymer, and on the incorporation of special nano-fillers in the polymer matrix. A blend of polyurethane (PU) and poly [ethylene-co-(methyl acrylate)-co-(glycidyl methacrylate) (PEMG) obtained from a simple solution method leads to lower values of Young modulus but also lower dielectric permittivities. The PU-PEMG blend presents however an improvement of the electromechanical capabilities, for example it is obtained a two fold increase of the strain at moderate fields with only 9%wt of PEMG.Two types of Polyetherblockamide (Pebax) are tested as polymer matrix. Very high values of permittivities are obtained particulary for Pebax1657 but accompanied for this material by high values of conductivity. Despite these high permittivities (more than 200000 for Pebax 1657 and 500 for Pebax 2533 at 0.1 Hz), only a moderate improvement of the electromechanical capability is observed compared to PU. We are also intererested on polyurethane nanocomposites based on silver nanoparticles coverered by PolyVinylPyrrolidone (PVP) polymer. A little polymer coating of the nanosilver leads to a better dispersion into the polyurethane films and higher values of permittivity. Different amounts of Ag-PVP are tested up to the percolation threshold close to 45%wt of fillers. Based on laser interferometer measurements and new cross characterization device, the optimal electromechanical properties are obtained for 20 %wt of Ag-PVP and a gain of 2 to 6 is obtained compared to pure polyurethane. In order to explain the difference between experimental and expected results and consequently to achieve a better understanding of the electromechanical behaviour of these different materials, some hypotheses were discussed and tested. We have shown particularly a drop of dielectric permittivities under electric fields for Pebax and nanocomposites, some problems of water absorption for Pebax and a decrease of crystallinity for the PU-Ag nanocomposites.

Abstract When producing ferrochrome, a submerged arc furnace (SAF) is used. The charge of an SAF consists of chromite pellets, coke, lumpy ore and quartzite as a slag modifier. The charge is pre-heated before it descends into the SAF where the charge eventually reduces and melts. The electrical conductivity of the charge is important because, among other things, it affects the productivity of the furnace. The electrical conductivity of the charge should ideally be low on the higher parts of the furnace and high near the electrode tip. This is to ensure that the electric current path travels through the metal bath via arcing, which provides the most effective heat transfer. Another option for the current path would be through the solid feed material via ohmic conduction, but since this zone is less reactive, the heat energy would be mostly wasted. This work brings forth new information about the electrical behaviour of coke and chromite pellet is produced. The electrical conductivity was measured at room temperature for different simulated process conditions (different coke textures, different reduction degrees of chromite pellets, sulphur in atmosphere and replacing the coke used in chromite pellet production with charcoal). It was found out that unlike gasification with a CO/CO2 mixture, heat treatment at 950°C increased the degree of graphitization and changed the electrical behaviour of coke. Furthermore, it was observed that increasing the chromite pellets’ reduction degree reduced the electrical conductivity measured at room temperature. In the case of chromite pellets and sulphur in the atmosphere it was found that sulphur has an effect on the pellets’ electrical behavior and structure during reduction, which - in turn - has an effect on the SAF performance when raw materials with varying sulphur contents are used. Lastly, it was found that substituting coke with charcoal when producing chromite pellets affects the sintering behaviour, cold compression strength, and electrical conductivity of the chromite pellets. / Tiivistelmä Uppokaariuuni on osa ferrokromin valmistusprosessia. Uppokaariuuniin panostetaan kromiittipellejä, koksia, palarikastetta ja kvartsiittia. Etukuumennusuunista panos laskeutuu uppokaariuuniin, jossa se pelkistyy ja lopulta sulaa. Uppokaariuunin panoksen sähkönjohtavuus on tärkeää uunin toiminnan kannalta, koska se vaikuttaa suoraan esimerkiksi tuottavuuteen. Jotta virran kulku tapahtuisi optimaalisesti sulan metallin kautta, panoksen sähkönjohtavuuden tulee olla pieni uunin yläosissa ja suuri alaosassa lähellä elektrodien päitä. Mikäli virran kulku tapahtuu uunin yläosassa, hukataan lämpöenergiaa ja uunin toiminta hankaloituu. Tässä työssä on selvitetty koksin ja kromiittipellettien sähköisiä ominaisuuksia. Sähkönjohtavuutta on tutkittu useilla simuloiduilla prosessiolosuhteilla (koksin eri tekstuurit, kromiittipellettien eri pelkistysasteet, rikin pitoisuus atmosfäärissä ja kromiittipellettien valmistuksessa on korvattu koksi puuhiilellä). Nämä mittaukset on tehty huonelämpötilassa. Huomattiin, että toisin kuin koksin kaasutus, koksin lämpökäsittely (950°C) nosti grafitoitumisastetta ja vaikutti sähköisiin ominaisuuksiin. Kromiittipelletin pelkistymisasteen noustessa huonelämpötilassa mitattu sähkönjohtavuus laski. Kun kromiittipelletit altistetaan atmosfäärille, jossa on rikkiä, pellettien sähköiset ominaisuudet muuttuvat samoin kuin rakenne pelkistyksen aikana. Tämä vaikuttaa uppokaariuunin toimintaan, kun käytetään raaka-aineita, joissa rikkipitoisuus vaihtelee. Kun kromiittipellettien valmistuksessa käytettävä koksi korvataan puuhiilellä, tämä vaikuttaa sintrausprosessiin, kylmälujuuteen ja sähköisiin ominaisuuksiin.

This thesis aims to determine the distribution of the relative permittivity for random mixtures of material using electromagnetic simulations. The algorithm used in the simulations is the FDTD method which solves Maxwell's equations numerically in the time-domain. The material is modeled as randomly shaped particles with radius 12 ± 10 micrometre in x- and y-direction and radius 3 ± 1 micrometre in zdirection. The scattering parameters from the transmitted and reflected electric field when a plane wave interacts with the material are measured. The relative permittivity is determined from the scattering parameters using the iterative Baker-Jarvis method. The simulations shows that both the distribution and the value of the relative permittivity is low when the particles have non conducting layers to force interruptions to prevent percolation, a conducting path between the particles. The most important result is of the kind where the simulations do not have any boundaries to prevent percolation. These simulations reflects how the relative permittivity distributes in real measurements. It is established that the value of the relative permittivity has a large distribution and also that percolation occurs because of the periodic structures.

Le titanate de baryum et de strontium (BaSrTiO3) est un matériau diélectrique de synthèse à forte permittivité possédant la propriété d'être accordable lorsqu'il est soumis à un champ électrique. Ceci est lié à sa structure cristalline à maille perovskite. Son intégration dans des dispositifs capacitifs est donc prometteuse pour l'industrie de la microélectronique. Il est déposé en couches minces par pulvérisation cathodique à partir de cibles pressées à froid au sein du laboratoire. L'étude de la croissance du matériau, dopé ou non, et de ses propriétés électriques à 100 khz ont permis d'envisager une montée en fréquence. Les évolutions de la permittivité diélectrique complexe et de l'accordabilité du matériau ont ainsi pu être étudiées sur un dispositif spécifique dans une gamme de fréquences allant de 1 à 60 ghz. L'utilisation d'un logiciel de simulation numérique par éléments finis (ELFI) dans le cadre de l'étude à haute fréquence permet de remonter aux caractéristiques propres du matériau, et ainsi d'interpréter plus finement les résultats issus de l'étude en basse fréquence. L'ensemble des connaissances acquises permet finalement de développer des dispositifs à capacité variable qui sont actuellement en cours d'élaboration au sein du laboratoire. / The barium and strontium titanate (BST) is a human made dielectric material with a high dielectric constant which is tunable once submitted to an electric field. This is due to its crystalline structure based on a perovkite mesh. Its integration into capacitive devices is thus fully promising for microelectronic industry. The material is deposited by RF magnetron sputtering from cold pressed targets made in the laboratory. Studying the growth of the material, doped or not, and its electrical properties at 100 kHz has allowed increasing frequency. The variations of the complex permittivity and tunability have thus been studied on a range of frequencies from 1 to 60 GHz. Using the numerical simulation software Elfi enables one to get a good estimation of the intrinsic properties of BST and a sharper explanation of the results obtained at low frequencies. This knowledge finally allows engineering in varactor devices, which is now in progress.

In recent years, there has been an increasing interest on left handed metamaterials because of their possible innovative applications. The pioneer study introducing such materials was brought out by V. G. Veselago in 1968 [1]. In his work, Veselago proposed a medium having simultaneously negative electric permittivity and magnetic permeability and investigated its electromagnetic characteristics. He found out that the electric field, magnetic field and the propagation vector form a left handed triplet, thus named such materials as &ldquo / Left Handed Materials&rdquo / . Despite the significance of Veselago&rsquo / s inferences, the metamaterial theory stayed dormant for nearly 30 years. Towards the end of 1990s, the physically realizable left handed materials were built as the combination of two periodical structures / Split Ring Resonators (SRRs) and metallic thin wire arrays [4-5]. In this thesis, electrical and magnetic characteristics of the left handed metamaterials are theoretically investigated by using the analytical models for their permittivity and permeability functions with respect to frequency. For this purpose, first, two basic metamaterial structures / the Split Ring Resonators and Thin Metallic Wire Arrays are studied individually and their electrical and magnetic characteristics are examined. Finally, the composite left handed structure containing both SRRs and thin wires is studied to investigate the resulting simultaneous resonance properties and to estimate their overall effective permeability and permittivity functions.

Organic materials are ubiquitous in the geologic environment, and can exert significant influence over the interfacial properties of minerals. However, due to the complexity in their structure and interaction with soil solids, their impact has remained relatively unquantified. This study investigated the engineering behaviors of organoclays, which were synthesized in the laboratory using naturally occurring clay minerals and quaternary ammonium compounds of controlled structure and density of loading. Organic cations were chosen to study the effects of functional group structure and size. The laboratory investigation showed that the presence of the organic cations on the mineral surfaces led to increased hydrophobicity of all clays tested. Conduction studies on the electrical, hydraulic, and thermal properties of the organoclay composites suggested that increasing the total organic carbon content resulted in decreased electrical and thermal conductivity, but increased hydraulic conductivity, due to the reduced swelling of the base clay mineral phase. Electrokinetic properties of the organoclays illustrated that compared with the clay's naturally occurring inorganic cations, exchanged quaternary ammonium cations were more likely bound within a particle's shear plane. Consequently, organoclays had less negative zeta potential than that of unmodified bentonite. Increasing the length of one carbon tail was more effective at binding organic cations within the shear plane than increasing the size of the cation, when compared on the basis of total organic carbon content. In terms of large strain strength, the modified organic clays exhibited increased shear strength, in part owing to the reduction in water content caused by the presence of the hydrophobic organic layering. Shear strength increased with single carbon tail length or with cation size, although the latter effect tended to reach a plateau as the length of the four short cation tails increased from 2 to 4. In terms of small strain behavior, the shear modulus was shown to be a function of the total organic carbon content. It is believed that number of particle contacts increased as the organic carbon content increased. Stiffness increased as either the size of the cation or the total organic carbon content was increased. Damping also increased as the organic loading was increased, with the organic phase acting as an energy dissipation mechanism.

Recent research focuses on expanding the use of RF/Microwave circuits and systems to include multi-disciplinary applications. One example is the detection of the dielectric properties of chemicals and bio-chemicals at microwave frequencies, which is useful for pharmaceutical applications, food and drug safety, medical diagnosis and material characterization. Dielectric spectroscopy is also quite relevant to detect the frequency dispersive characteristics of materials over a wide frequency range for more accurate detection. In this dissertation, on-chip and on-board solutions for microwave chemical sensing are proposed. An example of an on-chip dielectric detection technique for chemical sensing is presented. An on-chip sensing capacitor, whose capacitance changes when exposed to material under test (MUT), is a part of an LC voltage-controlled oscillator (VCO). The VCO is embedded inside a frequency synthesizer to convert the change in the free runing frequency frequency of the VCO into a change of its input voltage. The system is implemented using 90 nm CMOS technology and the permittivities of MUTs are evaluated using a unique detection procedure in the 7-9 GHz frequency range with an accuracy of 3.7% in an area of 2.5 × 2.5 mm^2 with a power consumption of 16.5 mW. The system is also used for binary mixture detection with a fractional volume accuracy of 1-2%. An on-board miniaturized dielectric spectroscopy system for permittivity detec- tion is also presented. The sensor is based on the detection of the phase difference be- tween the input and output signals of cascaded broadband True-Time-Delay (TTD) cells. The sensing capacitor exposed to MUTs is a part of the TTD cell. The change of the permittivity results in a change of the phase of the microwave signal passing through the TTD cell. The system is fabricated on Rogers Duroid substrates with a total area of 8 × 7.2 cm2. The permittivities of MUTs are detected in the 1-8 GHz frequency range with a detection accuracy of 2%. Also, the sensor is used to extract the fractional volumes of mixtures with accuracy down to 1%. Additionally, multi-band and multi-standard communication systems motivate the trend to develop broadband front-ends covering all the standards for low cost and reduced chip area. Broadband amplifiers are key building blocks in wideband front-ends. A broadband resistive feedback low-noise amplifier (LNA) is presented using a composite cross-coupled CMOS pair for a higher gain and reduced noise figure. The LNA is implemented using 90 nm CMOS technology consuming 18 mW in an area of 0.06 mm2. The LNA shows a gain of 21 dB in the 2-2300 MHz frequency range, a minimum noise figure of 1.4 dB with an IIP3 of -1.5 dBm. Also, a four-stage distributed amplifier is presented providing bandwidth extension with 1-dB flat gain response up to 16 GHz. The flat extended bandwidth is provided using coupled inductors in the gate line with series peaking inductors in the cascode gain stages. The amplifier is fabricated using 180 nm CMOS technology in an area of 1.19 mm2 achieving a power gain of 10 dB, return losses better than 16 dB, noise figure of 3.6-4.9 dB and IIP3 of 0 dBm with 21 mW power consumption. All the implemented circuits and systems in this dissertation are validated, demonstrated and published in several IEEE Journals and Conferences.

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