Ce travail de thèse a pour objectif la caractérisation des propriétés physico-chimiques descéramiques de composition (1-x) BaTi0.8Zr0.2O3-x Ba0.7Ca0.3TiO3 préparées par frittage conventionnelet frittage flash (SPS). Les études structurales réalisées au voisinage du point triple (x≈ 0.32) à l’aidede la diffraction des RX de haute résolution (synchrotron) sur poudre ont introduit des modificationsmajeures sur le diagramme de phase température-composition déjà proposé. La réponseélectromécanique géante mesurée est alors corrélée à la dégénérescence du profil de l’énergie libreinduite par les instabilités structurales. De plus, la flexibilité de la polarisation sous contraintesthermique et électrique est couplée à un assouplissement de la maille cristalline. Ces deuxcaractéristiques contribuent ensemble à une réponse électromécanique colossale via une forteactivité des murs de domaine. La dégradation des propriétés diélectriques, ferroélectriques etpiézoélectriques pour les céramiques BCTZ (x=0.32 et 0.5) élaborées par frittage flash estessentiellement attribuée aux fluctuations importantes de composition et à la stabilisation de laconfiguration des murs de domaines avec la diminution de la taille des grains. / The aim of this work is to make a full characterization of the structural, microstructural, dielectric,ferroelectric and piezoelectric properties of the perovskite-structured oxides (1-x) BaTi0.8Zr0.2O3-xBa0.7Ca0.3TiO3 prepared by a conventional solid-state reaction method (conventional sintering) andSPS fabrication technique. Using high-resolution synchrotron x-ray powder diffraction, the structuralinvestigations carried out close to the triple point (x≈ 0.32) have introduced significant corrections tothe previously published composition-temperature phase diagram. The colossal electromechanicalresponse was then correlated to a strongly degenerate free energy landscape caused by structuralinstabilities. Furthermore, the coupling between the high polarization flexibility under electric andthermal stresses and the ‘lattice softening’ gives rise to a giant electromechanical response due tohigh domain wall activities. The decrease of the dielectric, ferroelectric and piezoelectric propertiesof BCTZ ceramics (x=0.32 and 0.5) processed by SPS was essentially attributed to the largecompositional fluctuations and stable domain wall configurations as the grain size decreased.

This thesis entails the utilisation of ab initio density functional theory (DFT) in conjunction with neutron and synchrotron spectroscopy to study the mechanical, vibrational, and dielectric response of metal-organic framework (MOF) materials at the molecular level. MOFs are crystalline materials with nanoscale porosity, which have garnered immense scientific and technological interest for a wide variety of innovative engineering applications. One part of the thesis involves using low-frequency lattice vibrations to characterise the various physical motions that are possible for framework materials. These collective modes detected at terahertz (THz) frequencies have been used to reveal a broad range of exciting possibilities. New evidence has been established to demonstrate that THz modes are intrinsically linked to anomalous elasticity underpinning gate-opening and pore-breathing mechanisms, and to shear-induced phase transitions and the onset of structural instability. The phenomenon of molecular rotor mechanisms and trampoline-like motions are also observed, along with the first experimental confirmation of coordinated shear dynamics. Additionally, a new method to characterise the effects of temperature, and hence thermally-induced structural amorphisation is reported. Finally, for the first time, the frequency-dependent (dynamic) dielectric response of MOF materials, across the extended infrared (IR) spectral region was reported. The results were obtained from experimental synchrotron radiation IR reflectivity and DFT to reveal the low-к dielectric response of MOFs and established structure-property trends that highlight them as promising systems for microelectronic device applications.

Electrical insulation papers are a widely used group of papers in insulation applications and has been used for more than 100 years. Common applications include use as the dielectric medium in capacitors and insulation material in cables, bushings and transformers. As new advances in the study of the electrical properties of paper are made, the prospects of future applications grow. One interesting prospect is the use of paper as a substrate in sensing devices, biodegradable, printed and flexible electronics. Paper is a renewable and recyclable material and it would therefor be desirable to replace non-renewables materials such as plastics with paper as e.g., substrate in printed electronics. For this to be feasible the paper must be able to meet the electric and dielectric requirements of the intended application, among which low dielectric losses is a key parameter. One way to alter and control the electric and dielectric properties of a paper sample is through the selection of different ions in the ion-exchange step of the paper making process. In a collaboration between KTH Royal Institute of Technology and RISE - Research Institutes of Sweden AB working within a greater Digital Cellulose Center (DCC) project, this thesis aims to measure and characterise the dielectric response of a set of novel ion-exchanged paper samples together with a set of reference papers currently used in electrical applications. The greater goal of RISE work is to understand and map the influence of ion choice in order to better understand and control the dielectric properties of paper. The samples were measured using an impedance spectroscopy method from which capacitance and permittivity can be calculated. A parallel plate Kelvin guard-ring capacitor consisting of two electrodes and a guard ring placed in a custom made climate controlled chamber was used to measure the samples in different environmental conditions. The results show that the choice of ion used in the ion-exchanged papers heavily influence the samples dielectric response, both its dielectric constant and dielectric losses. Further, the choice of ion valence appears correlated with the change in responses; monovalent ions had much greater influence than bivalent ions. This effect appears to stem from monovalent ions having a greater mobility within the bulk material, more research is however needed for a definite answer. / Elektriska isoleringspapper är en flitigt använd grupp av papper i isoleringsapplikationer och har använts i mer än 100 år. Vanliga applikationsområden inkluderar användning som dielektriskt medium i kondensatorer och isoleringsmaterial i kablar, genomföringar och transformatorer. I takt med att nya framsteg görs inom olika pappers elektriska egenskaper växer utsikterna för framtida tillämpningar. En intressant möjlighet är användningen av papper som substrat för sensorer, biologiskt nedbrytbar, tryckt och flexibel elektronik. Papper är ett förnybart och återvinningsbart material och det vore därför önskvärt att ersätta icke förnybara material som plast med papper som t.ex. substrat i tryckt elektronik. För att detta ska vara genomförbart måste papperet kunna uppfylla de elektriska och dielektriska kraven för den avsedda applikationen, bland vilka låga dielektriska förluster är en nyckelparameter. Ett sätt att ändra och kontrollera de elektriska och dielektriska egenskaperna hos ett pappersprov är genom valet av olika joner i jonbytessteget i papperstillverkningsprocessen. I ett samarbete mellan KTH Kungliga Tekniska Högskolan och RISE Research Institutes of Sweden AB som arbetar inom ett större Digital Cellulose Center-projekt, syftar denna avhandling till att mäta och karakterisera den dielektriska responsen hos en uppsättning nya jonbytta pappersprover tillsammans med en uppsättning referenspapper. Det övergripande målet i RISE arbete är att förstå och kartlägga påverkan av jonval för att bättre förstå och kontrollera pappers dielektriska egenskaper. Proverna mättes med en impedansbaserad mätmetod från vilken kapacitans och permittivitet kan beräknas. En Kelvin plattkondensator bestående av två elektroder och en skyddsring placerad i en skräddarsydd klimatkontrollerad kammare användes för att mäta proverna under olika miljöförhållanden. Resultaten visar att valet av jon som används i jonutbytet kraftigt påverkar provets dielektriska respons, både dess dielektriska konstant och dielektriska förluster. Vidare verkar valet av jonvalens vara korrelerat med förändringen i frekvenssvar; envärda joner hade mycket större inflytande än tvåvärda joner. Denna effekt verkar bero på att envärda joner har en större rörlighet inom bulkmaterialet, mer forskning krävs dock för ett definitivt svar.

First principle electronic structure theory is used to describe the effect of crystal binding on radiation detectors, electron transport properties, and structural damage induced by intense irradiation. A large database containing general electronic structure results to which data mining algorithms can be applied in the search for new functional materials, a case study is presented for scintillator detector materials. Inelastic cross sections for the generation of secondary electron cascades through impact ionization are derived from the dielectric response of an electron gas and evolved in time with Molecular Dynamics (MD). Qualitative and quantitive estimates are presented for the excitation and relaxation of a sample irradiated with Free Electron Laser pulses. A study is presented in where the structural damage on covalent bonded crystals following intense irradiation is derived from a Tight Binding approach and evolved in time with MD in where the evolution of the sample is derived from GW theory for the quasiparticle spectra and a dedicated Boltzmann transport equation for the impact ionization.

La plupart des matériaux ferroélectriques actuellement utilisés pour les applications industrielles sont des céramiques à base de plomb. De tels composés sont nocifs à l’environnement en raison de la toxicité et de la volatilité de l’oxyde de plomb durant le processus de préparation de ces matériaux. Dans le cadre du respect de l'environnement, la recherche de céramiques sans plomb ou de faible teneur en plomb ayant des propriétés équivalentes est devenue l'une des principales alternatives aux céramiques à base de plomb. C’est dans cette perspective que se situe le présent travail, focalisé sur l’investigation de matériaux de formules : Ba1-xPbx(Ti1-yZry)O3 (2.5% ≤ à x ≤ 10%) et Ba1-xEr2x/3Ti1-yZryO3. La synthèse par voie solide a été utilisée pour l’élaboration des matériaux. Les techniques expérimentales utilisées sont l’analyse thermogravimétrique, la dilatomètrie, la diffraction des rayons X, la microscopie électronique à balayage couplée à un système de microanalyse EDX et la spectrométrie d’impédance. L’utilisation de ces diverses techniques nous a permis d’optimiser les conditions d’élaboration et d’obtenir des céramiques denses de densité supérieures à 90%. Par ailleurs, les paramètres structuraux ont été affinés par la méthode de Rietveld puis discutés. En outre, ces céramiques possèdent des propriétés ferroélectriques classiques et/ou relaxeurs dont certaines ont des caractéristiques diélectriques très intéressantes au voisinage de la température ambiante. De telles compositions dépourvues de plomb ou contenant très peu de plomb permettent de limiter considérablement la pollution de l’environnement. Grâce à leurs bonnes performances diélectriques, ils pourraient être des candidats potentiels pour remplacer les matériaux à base de plomb actuellement usagés dans divers appareillages électroniques. / Most of ferroelectric materials currently used in the industrial applications are lead-based ceramics. Such compounds are harmful to the environment due to the toxicity and volatility of lead oxide during the preparation process of these materials. Therefore, environmental friendly lead-free ceramics or low-lead content materials with equivalent properties has become one of the main topics as an alternative to lead-based ceramics. In this view, the present work focuses on investigating materials with formulas :Ba1-xPbx(Ti1-yZry)O3 (2.5% ≤ x ≤ 10%) and Ba1-xEr2x/3(Ti1-yZry)O3.Solid state route was used for materials elaboration. The experimental techniques used are thermogravimetric analysis, dilatometry, X-ray diffraction, scanning electron microscopy coupled to an EDX microanalysis system and impedance spectrometry. The use of these various processes allowed us to optimize the synthesis conditions and to obtain dense ceramics with density superior to 90%. In addition, the structural parameters were refined by the Rietveld method and then discussed. Furthermore, these ceramics exhibited normal and/or relaxor ferroelectric properties then some of them have very interesting dielectric characteristics in the vicinity of room temperature. Such lead-free ceramics or low-lead content materials reduce significantly the environmental pollution. Due to their good dielectric performances, they could be potential candidates for replacing lead-based materials currently used in various electronic equipments.

The electrical properties of proteins in solution are important for their structure and function. Computational biophysics studies of proteins need accurate parameters to ensure that numerical simulations match physical reality. Past work in this eld has compared the electrical properties of proteins obtained from dielectric spectroscopy to numerical simulations of proteins in water with adjustment of pKa values to try to capture the inevitable changes in electrical conformation that will occur in a complex structure such as a folded protein. However, fundamental veri cation of the charge parameters of the amino acid building blocks in common molecular dynamics software packages with electrical experiments needs to be performed to have increased con dence in the results from numerical simulations. The aim of this thesis is to start from a fundamental building block, the single amino acid alanine, and to compare numerical simulations of this amino acid in water using parameters from commonly used charge structures in CHARMM, GROMOS, and OPLS, with electrical parameters obtained from dielectric spectroscopy experiments in the GHz range. To this end, multiple molecular dynamics simulations were performed to accurately determine how these different charge structures yield different dielectric increments. Additionally, a commercial RF dielectric measurement probe was modi ed to perform measurements on solutions containing alanine at different concentrations. Using regression, the dielectric increment of alanine is readily determined and compared with the numerical simulations. The results indicate that the CHARMM and OPLS parameters seem to adequately capture the charge con guration of alanine in solution, while the GROMOS parameters produce a dielectric increment but do not seem to adequately capture the charge con guration of alanine in solution. These studies lay the foundation for future studies of additional amino acids in solution as well as a stepping stone for larger simulations of the electrical properties of fully solvated proteins in solution.

Insulation in rotating machines is a common cause for failure. Therefore, research in the area is large and is important to further increase the knowledge of the phenomena related to insulation degradation. This thesis is a case study on 20 stator bars obtained from a generator that had been showing signs of insulation degradation while in operation. The insulation was investigated using a range of measurements to be able to evaluate the degradation of these bars. The measurements performed were electrical partial discharge measurements, acoustic partial discharge measurements, dielectric response measurements, and breakdown testing. Furthermore, a more scientific approach to the commonly used tap test in the industry was conducted, which has not been done before and the purpose was to validate this commonly used test method. It was concluded that the bars have a significant amount of partial discharges within them, and that the stress grading is likely to be blamed in many of the worst cases. Furthermore, the dielectric response measurements provided good information on the thermal stability of the insulation. The set-up of the tap test did not provide reasonable results, and the method approach as well as the experimental set-up was to blame for this. In future work, investigating this specific area could be beneficial. The electrical partial discharge measurements and the breakdown test provided unexpected results when compared, where the former indicated much degradation while the latter proved that the bars can withstand very high voltage levels. / Isolering i roterande maskiner är en vanlig orsak till fel. Forskningen på området är därför omfattande och viktig för att ytterligare öka kunskapen om fenomen som rör isoleringsnedbrytning. Denna avhandling är en fallstudie på 20 statorstänger som erhållits från en generator som hade visat tecken på isoleringsnedbrytning under drift. Isoleringen undersöktes med hjälp av en rad olika mätningar för att kunna utvärdera nedbrytningen av dessa stänger. De mätningar som utfördes var mätningar av elektriska partiella urladdningar, akustiska partiella urladdningar, mätningar av dielektrisk respons och genombrottstester. Dessutom genomfördes ett mer vetenskapligt tillvägagångssätt för det allmänt använda tapptestet i branschen, vilket inte har gjorts tidigare och syftet var att validera denna allmänt använda testmetod. Slutsatsen blev att stängerna har en betydande mängd partiella urladdningar i sig, och att spänningsgraderingen sannolikt får skulden i många av de värsta fallen. Dessutom gav mätningarna av den dielektriska responsen god information om isoleringens termiska stabilitet. Upplägget för tapptestet gav inte rimliga resultat, och detta berodde både på metodiken och på försöksupplägget. I framtida arbete kan det vara bra att undersöka detta specifika område. Mätningarna av den elektriska partiella urladdningen och genombrottstestet gav oväntade resultat när de jämfördes, där de förstnämnda visade på mycket försämring medan de sistnämnda bevisade att stängerna kan motstå mycket höga spänningsnivåer.