Les matériaux polymères sont largement utilisés en tant qu'isolants dans les domaines du génie électrique, de l'électronique de puissance et de la microélectronique. Ces diélectriques sont principalement en contact avec d'autres composants: avec des semi-conducteurs et des métaux dans les câbles haute tension, avec des substrats et d'autres diélectriques dans les systèmes multicouches. Ces interfaces sont omniprésentes, et contribuent à l'injection et l'accumulation de charges d'espace dans les diélectriques solides. D'autre part, au cours de leur vie, ils sont soumis à de nombreuses contraintes, de température, de champ... Ces contraintes peuvent conduire à la dégradation prématurée et à la rupture diélectrique du matériau par une distorsion du champ électrique, et conduire au dysfonctionnement du système. Des études antérieures, expérimentales et de simulations, ont montré l'importance des interfaces sur la génération de charges à l'intérieur du diélectrique, mais les approches théoriques comme la loi d'injection Schottky ne fournissent pas une description adéquate pour des courants expérimentaux. Cependant les recherches récentes montrent que les états de surface qui se forment à l'interface métal/isolant jouent un rôle important sur le comportement des diélectriques. L'injection de charges est principalement affectée par la nature du contact et des états de surface. L'enjeu de ce travail est de comprendre les phénomènes en jeu à une interface métal/isolant, afin de les modéliser correctement. Ce travail est basé sur une approche duale modélisation et expérience. L'isolant retenu est ici est le polyéthylène basse densité (LDPE). Dans un premier temps, nous avons caractérisé expérimentalement des interfaces métal/isolant. Dans un seconde temps, nous avons développé un modèle numérique capable de prendre en compte les états de surface. L'approche est originale, puisque l'étude porte sur l'injection et le transport de charges en tenant compte d'une distribution exponentielle des états d'énergie à l'interface.

L'étude des mécanismes fondamentaux qui contrôlent l'injection des électrons polarisés en spin à partir d'un métal ferromagnétique vers le silicium ainsi que l'interaction entre ces spins et l'aimantation d'une électrode ferromagnétique « collectrice » en spin, constitue le sujet de ce travail de thèse. Cette étude est basée sur l'analyse et la modélisation des caractéristiques électriques obtenues sur une structure « test » composée de deux électrodes ferromagnétiques servant respectivement à injecter et à collecter les électrons polarisés en spin. Une étude approfondie des propriétés électriques de la diode ferromagnétique/isolant/silicium (FMIS) est aussi réalisée. Le renversement sélectif de l'aimantation d'une des deux électrodes et la variation de la (magnéto-) résistance attendue fournissent un outil pour l'étude de l'injection de spins dans le silicium. Ce concept de mémoire magnétique intégrée sur silicium pourrait fournir à terme une solution alternative aux mémoires de type flash qui vont être de plus en plus confrontées au problème de rétention d'information.

Dans le cadre de l'homogénéisation, nous étudions des problèmes de transfert d'énergie posés dans un domaine solide perforé périodique où coexistent deux échelles d'espace (macroscopique et microscopique). Ces problèmes modélisent le transfert de chaleur par conduction dans le solide et par rayonnement au bord de chaque perforation. La présence du rayonnement implique des conditions aux limites non usuelles (vis à vis de la théorie de l'homogénéisation). Deux types de rayonnement sont considérés: rayonnement en milieu infini (condition non linéaire) et rayonnement en cavité à parois grises diffusantes (condition non linéaire et non locale). L'homogénéisation dans les deux cas conduit à un modèle de conduction posé dans un solide équivalent ayant! une conductivité effective qui prend en compte le rayonnement aux bords. Nous développons donc une méthodologie (homogénéisation et validation) basée sur une justification théorique du processus d'homogénéisation via la méthode de convergence à deux échelles et une validation numérique via des simulations au moyen du code de calcul CAST3M. Cette étude est menée dans le cadre de l'analyse de fonctionnement des réacteurs à caloporteur gaz. Les résultats sont également exploitables pour d'autres domaines perforés impliquant les phénomènes de transferts en question.

<p> The inverse heat conduction problem also frequently referred as the sideways heat equation, in short SHE, is considered as a mathematical model for a real application, where it is desirable for someone to determine the temperature on the surface of a body. Since the surface itself is inaccessible for measurements, one is restricted to use temperature data from the interior measurements. From a  mathematical point of view, the entire situation leads to a non-characteristic Cauchy problem, where by using recorded temperature one can solve a well-posed nonlinear problem in the finite region for computing heat flux, and consequently obtain the Cauchy data [u, u_x]. Further by using these data and by performing an appropriate method, e.g. a space marching method, one can eventually achieve the desired temperature at x = 0.</p><p>The problem is severely ill-posed in the sense that the solution does not depend continuously on the data. The problem solved by two different methods, and for both cases we stabilize the computations by replacing the time derivative in the heat equation by a bounded operator. The first one, a spectral method based on finite Fourier space is illustrated to supply an analytical approach for approximating the time derivative. In order to get a better accuracy in the numerical computation, we use cubic spline function for approximating the time derivative in the least squares sense.</p><p>The inverse problem we want to solve, by using Cauchy data, is a nonlinear heat conduction problem in one space dimension. Since the temperature data u = g(t) is recorded, e.g. by a thermocouple, it usually contains some perturbation in the data. Thus the solution can be severely ill-posed if the Cauchy data become very noisy. Two experiments are presented to test the proposed approach.</p>

Resistive random access memory (RRAM) is a non-volatile memory technology based on resistive switching in a dielectric or semiconductor sandwiched between two different metals. Also known as memristors, these devices are potential candidates for a next-generation replacement for flash memory. In this thesis, bipolar resistive switching is reported for the first time in solution-deposited zinc-tin-oxide (ZTO). The impact of the compliance current on device operation, including the SET and RESET voltages, pre-SET, RESET and post-RESET currents, the resistance ratio between the low and high resistance states, retention, and the endurance, is investigated for an isolated Al dot/ZTO/Ir blanket device and for Al/ZTO/Pt crossbar RRAM devices. A gradual forming process is devised to improve device stability and performance. It is found that the device performance depends critically on the compliance current density that is used to limit the breakdown conduction during the SET operation. In addition, it was found that the conduction and switching mechanisms are consistent with the filament model of formation and rupture of conductive filaments. / Graduation date: 2012

The inverse heat conduction problem also frequently referred as the sideways heat equation, in short SHE, is considered as a mathematical model for a real application, where it is desirable for someone to determine the temperature on the surface of a body. Since the surface itself is inaccessible for measurements, one is restricted to use temperature data from the interior measurements. From a  mathematical point of view, the entire situation leads to a non-characteristic Cauchy problem, where by using recorded temperature one can solve a well-posed nonlinear problem in the finite region for computing heat flux, and consequently obtain the Cauchy data [u, ux]. Further by using these data and by performing an appropriate method, e.g. a space marching method, one can eventually achieve the desired temperature at x = 0. The problem is severely ill-posed in the sense that the solution does not depend continuously on the data. The problem solved by two different methods, and for both cases we stabilize the computations by replacing the time derivative in the heat equation by a bounded operator. The first one, a spectral method based on finite Fourier space is illustrated to supply an analytical approach for approximating the time derivative. In order to get a better accuracy in the numerical computation, we use cubic spline function for approximating the time derivative in the least squares sense. The inverse problem we want to solve, by using Cauchy data, is a nonlinear heat conduction problem in one space dimension. Since the temperature data u = g(t) is recorded, e.g. by a thermocouple, it usually contains some perturbation in the data. Thus the solution can be severely ill-posed if the Cauchy data become very noisy. Two experiments are presented to test the proposed approach.

The main objective of this industrially important work was to gain an increasing understanding of the properties of some industrially important materials such as CMSX-4 nickel base super alloy, 90Ti.6Al.4V alloy, 25Cr:6Ni stainless steel, 0.7% carbon steel, AISI 304 stainless steel-alumina composites, mould powder used in continuous casting of steel as well as coke used in blast furnace with special reference to the thermal diffusivities. The measurements were carried out in a wide temperature range covering solid, liquid, glassy and crystalline states. For CMSX-4 alloy, the thermal conductivities were calculated from the experimental thermal diffusivities. Both the diffusivities and conductivities were found to increase with increasing temperature. Microscopic analysis showed the presence of intermetallic phases γ´ such as Ni3Al below 1253 K. In this region, the mean free path of the electrons and phonons is likely to be limited by scattering against lattice defects. Between 1253 K and solidus temperature, these phases dissolved in the alloy adding to the impurities in the matrix, which, in turn, caused a decrease in the thermal diffusivity. This effect was confirmed by annealing the samples at 1573 K. The thermal diffusivities of the annealed samples measured at 1277, 1403 and 1531 K were found to be lower than the thermal diffusivities of non-annealed samples and the values did not show any noticeable change with time. It could be related to the attainment of equilibrium with the completion of the dissolution of γ´ phase during the annealing process. Liquid CMSX-4 does not show any change of thermal diffusivity with temperature. It may be attributed to the decrease of the mean free path being shorter than characteristic distance between two neighbouring atoms. Same tendency could be observed in the case of 90Ti.6Al.4V alloy. Since the thermal diffusivity increases with increasing temperature below 1225 K and shows slight decrease or constancy at higher temperature. For 25Cr:6Ni stainless steel, the thermal diffusivity is nearly constant up to about 700 K. Beyond that, there is an increase with temperature both during heating as well as cooling cycle. On the other hand, the slope of the curve increases above 950 K, which can be due to the increase of bcc phase in the structure. 0.7% carbon steel shows a decrease in the thermal diffusivity at temperature below Curie point, where the structure contains bcc+ fcc phases. Above this point the thermal diffusivity increases, where the structure contains only fcc phase. The experimental thermal conductivity values of these alloys show good agreement with the calculated values using Mills model. Thermal diffusivity measurements as a function of temperature of sintered AISI 304 stainless steel-alumina composites having various composition, viz, 0.001, 0.01, 0.1, 1, 2, 3, 5, 7, 8 and 10 wt% Al2O3 were carried out in the present work. The thermal diffusivity as well as the thermal conductivity were found to increase with temperature for all composite specimens. The thermal diffusivity/conductivity decreases with increasing weight fraction of alumina in the composites. The experimental results are in good agreement with simple rule of mixture, Eucken equation and developed Ohm´s law model at weight fraction of alumina below 5 wt%. Beyond this, the thermal diffusivity/ conductivity exhibits a high discrepancy probably due to the agglomeration of alumina particles during cold pressing and sintering. On the other hand, thermal diffusivities of industrial mould flux having glassy and crystalline states decrease with increasing temperature at lower temperature and are constant at higher temperature except for one glassy sample. The thermal diffusivity is increased with increasing crystallisation degree of mould flux, which is expected from theoretical considerations. Analogously, the thermal diffusivity measurements of mould flux do not show any significant change with temperature in liquid state. It is likely to be due to the silicate network being largely broken down. In the case of coke, the sample taken from deeper level of the pilot blast furnace is found to have larger thermal diffusivity. This can be correlated to the average crystallite size along the structural c-axis, Lc, which is indicative of the higher degree of graphitisation. This was also confirmed by XRD measurements of the different coke samples. The degree of graphitisation was found to increase with increasing temperature. Further, XRD and heat capacity measurements of coke samples taken from different levels in the shaft of the pilot blast furnace show that the graphitisation of coke was instantaneous between 973 and 1473 K. / QC 20100629

Das thermische Raummodell THERAKLES berechnet das dynamische Verhalten eines Raumes und seiner Umschließungsflächen in Abhängigkeit von realistischen Klimarandbedingungen, sowie Nutzer- und Anlagenverhalten. Neben Energieverbrauchswerten werden die operative Temperatur sowie weitere Kriterien zur Beurteilung der Behaglichkeit berechnet. Schwerpunkt der Anwendung liegt auf Optimierung der thermischen Behaglichkeit im Sommerfall, sowie energetischer Optimierung der Regelung von Heizungsanlagen unter Ausnutzung der Dynamik schwerer Baukonstruktionen und Massivbauwände. Das Modell beschreibt das dynamische Verhalten der Umfassungskonstruktionen durch instationäre, räumlich aufgelöste Simulation der Wand-, Fußboden-, und Decken- bzw. Dachflächen. Dadurch werden in der Konstruktion enthaltene Phasenwechselmaterialien (PCM) berücksichtigt und die zeitliche Verfügbarkeit der zusätzlichen Wärmespeicherfähigkeit abgebildet.

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An alternate family of “high” voltage (where the equilibrium voltage lies between 3.6 V and 4.2 V) polyanion cathode materials is reported in this thesis with the objective of improving specific energy density (Wh/kg) and developing a better understanding of polyanion electrochemistry. The electrochemical properties, synthesis and the structure of novel fluorosulfate materials crystallizing in the tavorite and the triplite type mineral structures are described. These materials display highest discharge voltages reported for any Fe2+/Fe3+ redox couple. LiFeSO4F was prepared in both the tavorite and the triplite polymorphs using inexpensive and scalable methods. Complete structural characterization was performed using X-ray and neutron based diffraction methods. A rapid synthesis of fluorosulfates can be achieved by using microwave heating. The local rapid heating created by the microwaves generates nanocrystalline LiFeSO4F tavorite with defects that induce significant microstrain. To date, this is unique to the microwave synthesis method. Phase transformation to the more stable triplite framework, facilitated by the lattice defects which include hydroxyl groups, is therefore easily triggered. The formation of nanocrystalline tavorite leads to nanocrystalline triplite, which greatly favors its electrochemical performance because of the inherently disordered nature of the triplite structure. Direct synthesis of the electrochemically active triplite type compound can be carried out either by extending the duration of the solvothermal reactions or by the partial substitution of Fe by Mn to produce LiFe1-xMnxSO4F. This study, overall, has led to a better understanding of the transformation of tavorite to the triplite phase. To examine Li and the Na ion conduction and their correlation with the electrochemical performance of 3-D, 2-D and 1-D ion conductors, atomistic scale simulations have been used to investigate tavorite type LiFeSO4F, NaFeSO4F, olivine type NaMPO4 (M= Fe, Mn, Fe0.5Mn0.5) and layered Na2FePO4F. These calculations predict high mobility of the Li-ion in the tavorite type LiFeSO4F but sluggish Na-ion transport in iso-structural NaFeSO4F. High mobility of the Na-ion is predicted for phosphate layered and olivine structures. Finally, the synthesis and structural details of NaMSO4F (M=Fe, Mn) and NH4MSO4F (M=Fe, Mn) are presented in the last chapter to show the structural diversity present in the fluorosulfate family.