Lithium-Ionen-Batterien besitzen ein ausgezeichnetes Potential für die Energiespeicherung. Das derzeit dominierende Anodenmaterial in Lithium-Ionen-Batterien mit einer Energiespeicherkapazität von 339 mAh/g ist Graphit. Als Alternative hierfür bieten sich Lithiumsilicide und Lithiumstannide an. Diese Materialien zeichnen sich durch eine viel größere Speicherkapazität und geringere Selbstentladungspotentiale aus. Für die kommerzielle Anwendung dieser beiden Systeme in Lithium-Ionen-Batterien werden grundlegende und verlässliche thermodynamische Daten benötigt. Derzeit ist die Existenz von sieben Lithiumsiliciden sicher nachgewiesen. Dazu zählen die sechs stabilen Phasen Li17Si4, Li16.42Si4, Li13Si4, Li7Si3, Li12Si7, die Hochdruckphase LiSi und die metastabile Phase Li15Si4. Für die ersten fünf genannten Phasen wurden in der ersten Förderperiode des Schwerpunktprogrammes 1473 Wärmekapazitäten und Standardentropien bestimmt. Bei den Lithiumstanniden sind derzeit sieben Phasen gesichert belegt. Allerdings existiert für keine Phase der Lithiumstannide ein verlässlicher thermodynamischer Basisdatensatz. Aus diesem Grund wurden für die beiden zuletzt genannten Lithiumsilicide (Li15Si4 und LiSi), sowie für die Lithiumstannide Li17Sn4, Li7Sn2, Li13Sn5 und Li7Sn3 die fehlenden thermodynamischen Daten experimentell bestimmt. Die hergestellten Phasen wurden zunächst mittels Röntgenbeugung, thermischer und chemischer Analyse charakterisiert. Ein Schwerpunkt dieser Arbeit lag auf der experimentellen Bestimmung der Wärmekapazitäten in einem Temperaturbereich von 2 K bis zur jeweiligen Zersetzungstemperatur der untersuchten Verbindungen. Hierfür wurden zwei unterschiedliche Kalorimeter verwendet: ein Physical Property Measurement System (Quantum Design) von 2 K bis 300 K und eine DSC 111 (Setaram), beginnend ab 300 K. Die experimentellen Daten konnten mit Messunsicherheiten von 1 % bis 2 % über 20 K und bis zu 20 % unterhalb von 20 K angegeben werden. Die Messungen bei niedrigen Temperaturen erlauben zudem die Berechnung der Standardentropien, sowie die Bestimmung von elektronischen Beiträgen und Gitterschwingungsbeiträgen zur Wärmekapazität. Weiterhin ist Fokus dieser Arbeit die Bestimmung der Standardbildungsenthalpien der Lithiumsilicide und Lithiumstannide auf Basis von Wasserstoffsorptionsmessungen mittels einer Sieverts-Apparatur. Hierfür wurden erstmals Messungen an den Lithiumsiliciden ausgehend von Li17Si4, LiH:Si (Li:Si = 17:4), Li16.42Si4 und LiSi durchgeführt. Für die Lithiumstannide dienten als Ausgangsmaterial Li17Sn4, LiH:Sn (Li:Sn =17:4), sowie Li7Sn2 und LiH:Sn (Li:Sn = 7:2). Die Anwendung des van´t-Hoff-Plots resultierte in Messunsicherheiten von mindestens 10 %. Aus diesem Grund wurde eine alternative Auswertemethode gewählt, bei der die ermittelten Wärmekapazitäten und Standardentropien mit den Gleichgewichtsdrücken aus den Wasserstoffsorptionsmessungen miteinander verknüpft werden. Auf diese Weise konnten Standardbildungsenthalpien für die untersuchten Phasen mit Fehlern kleiner 1 % ermittelt werden. Aus den Ergebnissen dieser Arbeit resultierte ein vollständiger, gesicherter thermodynamischer Datensatz für das System Li-Si. Das berechnete Li-Si-Phasendiagramm ist im sehr guten Einklang mit experimentellen literaturbekannten Daten. Für die Lithiumstannide erfolgte eine Validierung der ermittelten thermodynamischen Werte. Die in dieser Arbeit erzielten Ergebnisse liefern einen wesentlichen Beitrag zur Verbesserung der Datenbasis für thermodynamische Berechnungen und für das Verständnis von Phasensequenzen und Gleichgewichten beim Einsatz von Lithiumsiliciden bzw. Lithiumstanniden als Anodenmaterialien in Lithium-Ionen-Batterien.

The thesis deals with the creation for a numerical model of a solar collector with a phase change material as a heat storage medium. The model was implemented in Python. Using the created model, design optimization of several problems was carried out with the use of selected methods of heuristic optimization. The results of the behaviour of the created model and of design optimization were then analysed and evaluated.

This thesis mainly deals with the prediction of temperature on the components and the PCB during reflow soldering. The theoretical part describes the particular solder reflow process, types of heat transfer and temperature profiles. The practical part is divided into forecasting temperatures if the conveyor is stopped and the temperature predictions when the conveyor is in motion. In both parts of the measured temperature is compared with the predicted temperatures, which show the success rate of prediction. The last part of this work is part of the simulation, which helps in proper understanding of the issues discussed.

Half-metallic ferromagnets (HMFs), with fully spin-polarized conduction electrons, are prime candidates for optimizing spintronic devices. Many Heusler compounds (a class of ternary and quaternary intermetallics) are predicted to be HMFs, in particular Co$_{2}YZ$ (where $Y$ is usually another transition metal, and $Z$ is an s-p element). Crystal structure is controlled by thermodynamics to a large extent. Ideally, one should be able to control and optimize properties which are of interest by appropriately "tuning" the structure (e.g. annealing), but first one must understand the structure and its relation to observed physical properties. A local structural probe technique such as nuclear magnetic resonance (NMR) is an essential tool for identifying and quantifying the various atomic-scale orderings. Different Heusler structure types and antisite disorders affect the material's physical properties. In this thesis, order-disorder phenomena in both bulk and thin film samples of Co$_2$Mn$_{1-x}$Si$_x$ and Co$_2$Mn$_{1-x}$Fe$_x$Si have been systematically studied using NMR. Though it is the films which are directly implemented in actual devices, studying bulk samples as model systems provides invaluable information regarding the material properties. The evolution of local atomic structure in numerous thin films has been shown to depend greatly on preparation parameters, including post-deposition annealing temperature, and specific stoichiometry. For Co$_2$MnSi films, the ideal post-annealing temperature for promoting the $L2_1$ atomic structure was found; the threshold temperature above which structure continues to become higher-ordered in the bulk, but where too much interdiffusion at the buffer interface occurs, degrading the smooth interfaces necessary for high magnetoresistance ratios. NMR also adds evidence that Co$_2$Mn$_x$Si$_{0.88}$ ($x>$1) electrodes in magnetic tunnel junctions have highest tunneling magneto-resistance because the excess Mn suppresses the formation of detrimental Co$_{Mn}$ antisites. A systematic investigation of several thermal and magnetic properties, including Sommerfeld coefficients, Debye temperatures, saturation magnetic moments, spin-wave stiffness, and magnon specific heat coefficient, were measured for selected Co$_2$-based ternary and quaternary Heusler compounds. Obtained values were compared with theoretical ones calculated using electronic band structure methods. It has been systematically shown that adding a magnon term to the specific heat has a negligible effect on the electronic contribution in all cases.

Die vorliegende Dissertation stellt die experimentelle Bestimmung von grundlegenden thermodynamischen und kinetischen Stoffdaten im System Lithium-Silicium vor. Ausgehend von der Synthese qualitativ hochwertiger Lithiumsilicide wurden Wärmekapazitäten über einen großen Temperaturbereich (2-873 K) bestimmt, die aufgrund der Ergebnisse bei tiefen Temperaturen die Ermittlung weiterer Parameter wie beispielsweise der Standardentropien bzw. der Bildungsentropien der Lithiumsilicide ermöglichte. Die Eigenschaft der Silicide, mit Wasserstoff Verbindungen einzugehen, führte zudem zur Ausdehnung der Untersuchungen auf das System Li-Si-H. Aus der Erweiterung resultierte neben der formalkinetischen Beschreibung ablaufender Gleichgewichtsreaktionen die Bestimmung von Bildungsenthalpien der Silicide. Auf Grundlage der experimentell bestimmten Stoffgrößen (Cp, S°, ∆BH°), die für theoretische und praxisrelevante Berechnungen sehr verlässliche Stoffdaten darstellen, wurden thermodynamische Modellierungen im stofflichen System durchgeführt.

Functionally graded materials (FGMs) are inhomogeneous materials in which the material properties vary with respect to space. Research has been done by scientific community in developing techniques like photothermal radiometry (PTR) to measure the thermal conductivity and volumetric heat capacity of FGMs. One of the problems involved in the technique is to solve the inverse problem, i.e., estimating the thermal properties after the frequency scan has been obtained. The present work involves finding the unknown thermal conductivity and volumetric heat capacity of the FGMs by using finite volume method. By taking the flux entering the sample as periodic and solving the discretized 1-D thermal wave field equation at a frequency domain, one can obtain the complex temperatures at the surface of the sample for each frequency. These complex temperatures when solved for a range of frequencies gives the phase vs frequency scan which can then be compared to original frequency scan obtained from the PTR experiment by using a residual function. Brute force and gradient descent optimization methods have been implemented to estimate the unknown thermal conductivity and volumetric specific heat of the FGMs through minimization of the residual function. In general, the spatial composition profile of the FGMs can be approximated by using a smooth curve. Three functional forms namely Arctangent curve, Hermite curve, and Bezier curve are used in approximating the thermal conductivity and volumetric heat capacity distributions in the FGMs. The use of Hermite and Bezier curves gives the flexibility to control the slope of the curve i.e. the thermal property distribution along the thickness of the sample. Two-layered samples with constant thermal properties and three layered samples in which one of the layer has varying thermal properties with respect to thickness are considered. The program is written in Fortran and several test runs are performed. Results obtained are close to the original thermal property values with some deviation based on the stopping criteria used in the gradient descent algorithm. Calculating the gradients at each iteration takes considerable amount of time and if these gradient values are already available, the problem can be solved at a faster rate. One of the methods is extending automatic differentiation to complex numbers and calculating the gradient values ahead; this is left for future work.

Nous avons développé un modèle prédictif, utilisant le principe de contribution de groupes, pour prédire avec précision, le comportement des fluides pétroliers. Ce modèle baptisé PPR78 utilise l’équation d’état de Peng et Robinson et des règles de mélange de type Van der Waals avec un coefficient d’interaction binaire kij, dépendant de la température. De telles règles de mélange sont équivalentes à celles obtenues en combinant à compacité constante une fonction d’excès de type Van Laar et une équation d’état cubique.La première partie de cette étude a consisté à étendre le domaine d’application du modèle PPR78 aux systèmes contenant de l’eau, des alcènes et de l’hydrogène, en définissant six nouveaux groupes élémentaires. Une bonne précision du modèle est obtenue pour décrire les équilibres de phases de systèmes binaires impliquant ces constituants, notamment pour les systèmes présentant des diagrammes de phases de Type I et de Type II. Dans la deuxième partie l’ensemble des paramètres de groupes ont été réajustés, non seulement sur des données d’équilibres de phases mais également sur des données de grandeur de mélange. L’avantage de ce nouveau modèle E-PPR78 est qu’il permet de restituer les équilibres de phases avec une précision équivalente au modèle original et qu’il conduit à une très nette amélioration de la prédiction des enthalpies d’excès et des capacités calorifiques d’excès. / We have developed a predictive model, by means of a group contribution method, in order to predict with accuracy, the behavior of petroleum fluids. The model called PPR78 uses the Peng-Robinson equation of state and Van der Waals-type mixing rules with a temperature dependent binary interaction parameter kij. Such mixing rules are identical to those obtained by combining at constant packing fraction, a Van Laar-type excess function and a cubic equation of state.The first part of this study consisted in extending the application of the model PPR78 to systems containing water, alkenes and hydrogen, by defining six new elementary groups. The phase equilibria of binary systems involving these components are accurately described by the model, especially for the phase diagrams of Type I and Type II. In the second part, all the group parameters of the original model were re-fitted by using the phase equilibrium data, as well as the mixing property data. The advantage of this new model E-PPR78 is that it is capable to correlate the phase equilibria with an accuracy which is equivalent to the original model and it produces a very clear improvement in the prediction of excess enthalpies and excess heat capacities.

O entendimento dos princípios básicos do enovelamento proteico pode conduzir a muitas aplicações importantes. Embora não se conheçam todos os aspectos significativos envolvidos neste problema, experimentos e aproximações teóricas têm produzido avanços relevantes na sua compreensão, como, por exemplo, o papel dominante das forças hidrofóbicas. Com o propósito de contribuir para a identificação de alguns parâmetros determinantes no processo de folding, o objetivo deste trabalho consiste em estudar o potencial estéreo-hidrofóbico (isto é, o potencial hidrofóbico e um conjunto de especificidades estéricas adequadas) relacionado ao processo de enovelamento de proteínas globulares, evidenciando o papel das restrições estéricas e as características topológicas do estado nativo. Para tanto, empregou-se um modelo simplificado em rede cúbica, estudando-se, através de simulações Monte Carlo, o comportamento de mais de 40 cadeias tipo-proteínas, que apresentam estados nativos caracterizados pelos seguintes parâmetros topológicos: ordem de contato, χ, ordem de longo alcance e número φ de estruturas tipo grande manivela. Claramente, os resultados das simulações para as cadeias com configurações nativas, caracterizadas por baixo valor de χ e elevado valor de φ, são bastante diferenciados daqueles obtidos para as cadeias que apresentam configurações nativas com χ elevado e φ pequeno, evidenciando que o potencial estéreo-hidrofóbico, adotado neste trabalho, permite relacionar os comportamentos termodinâmico e cinético da cadeia tipo-proteína com os atributos topológicos da configuração nativa correspondente. Adicionalmente, mostrou-se que as restrições estéricas consideradas introduzem fortes mudanças na atividade configuracional, aumentando a estabilidade do estado nativo, bem como alterando, drasticamente, a curva da capacidade térmica, em função da temperatura, em comparação com os resultados das simulações obtidos com o potencial hidrofóbico (sem restrições estéricas). / The understanding of the basic principles of the protein folding process may lead to very important applications. Although all significant aspects of this problem are not yet known, experimental and theoretical results have given important contribution on the subject, as, for instance, about the dominant role of the hydrophobic forces. In order to contribute to the identification of significant ingredients for the folding process, the main goal of this work consists in studying the stereo-hydrophobic potential (that is, the hydrophobic potential and a set of steric specificities) related to the folding process of globular proteins, revealing the importance of the steric constraints and the role of the native structure. A minimalist lattice model was employed for this purpose, and more than forty distinct protein-like chains were studied. These chains were designed based on native structures characterized by topological parameters as contact order, χ, long range order and number φ of crankshaft-like structures. The Monte Carlo simulation results show clearly that the folding process depends strongly on the topological attributes of the native structure: thermodynamical and kinetic behavior for chains designed from native structures, presenting smaller χ and higher φ, are very distinguishable from those with higher χ and lower φ. Additionally it was shown that the steric constraints significantly modify the configurational activity, increasing the general conditions for the globule stability, as well changing drastically the shape of the thermal capacity behavior, as a function of the temperature, in comparison with the corresponding results obtained using the hydrophobic potential only, i.e., without the steric specificities.

No description available.

L’industrie de métallurgie est demandeuse de propriétés thermophysiques essentielles pour la modélisation et l’optimisation des procédés d’élaborations.Les propriétés thermophysiques des métaux et des alliages métalliques à l’état liquide sont mal connues. Ces propriétés dépendent de la température et sont difficiles à mesurer surtout à haute température. A l’état liquide, le métal est réactif et facilement polluable. Dans les années 1980, Egry a développé un lévitateur électromagnétique TEMPUS pour mesurer en apesanteur sans contact matériel les propriétés thermophysiques des métaux et alliages en fusion. Dans l’espace, les effets du brassage électromagnétique et de la déformation des échantillons fondus sont beaucoup plus faibles que sur terre.L’emploi de cet outil spatial est coûteux. C’est pour, à terme, diminuer les coûts tout en maintenant voire améliorant la qualité des mesures, que nous avons souhaité remplacer la microgravité par un champ magnétique continu.Les travaux réalisés dans cette thèse consistent à mesurer les propriétés thermiques des métaux par procédé électromagnétique en utilisant une méthode de calorimétrie modulée.Elle comporte deux parties.-Une partie numérique dans laquelle nous avons simulé d’une part le lévitateur spatial TEMPUS et d’autre part le lévitateur terrestre AEXAM.La simulation du lévitateur spatial TEMPUS a pour but de déterminer l’effet de la superposition de courants inducteurs de fréquences différentes (courants de chauffage et de centrage) sur les comportements hydrodynamique et thermique de la goutte. Les résultats des calculs nous ont montré que le courant de centrage est susceptible d’agir sur les mesures.La simulation du lévitateur terrestre AEXAM consiste à déterminer la fréquence d’oscillation verticale de la goutte, la puissance Joule dissipée dans celle-ci, les champs de vitesse et de température. La goutte prend la forme d’une poire et elle oscille à une fréquence de 7 Hz. La puissance Joule dissipée dans la charge est maximale vers le bas de la charge dans les premiers millimètres à mi-hauteur entre l’équateur et le pôle. Elle diminue en pénétrant dans la charge et est nul sur l’axe de symétrie. La convection dans la goutte crée un brassage électromagnétique et homogénéise le champ de température.-Une partie expérimentale dans laquelle le lévitateur AEXAM a été placé dans un champ magnétique continu horizontal pour amortir l’oscillation verticale et le brassage électro-magnétique de la goutte mentionnée dans les calculs. Ceci nous a permis la mise en œuvre d’un protocole de mesure original sur un métal liquide. Ce protocole est un programme de traitement des donnés basé sur le comportement du champ de température lorsque les sources thermiques internes à l’échantillon sont instationnaires. Dans ce programme, nous avons utilisé une fonction d’identification qui permet d’obtenir un modèle mathématique à partir de mesures. Pour obtenir un modèle mathématique consistant, il est important d'exciter le système avec toutes les fréquences de sa plage de fonctionnement. C’est ce que nous faisons quand nous appliquons un bruit blanc sur la consigne d’entrée du générateur. Nous avons précédemment validé le protocole sur du solide en remontant aux valeurs de la capacité calorifique et de la conductivité thermique.Pour optimiser les pertes de masse, les instabilités sur les mesures du courant inducteur et la bonne reproductivité des mesures sur une goutte, nous avons choisi une masse initiale de 3,5 g pour faire les mesures avec modulation du courant inducteur dans un champ magnétique continu de 1 Tesla. Nous avons obtenu les valeurs de la capacité calorifique et de la conductivité thermique de la goutte. Celles-ci sont voisines des valeurs données par la littérature. Ce qui nous a permis de valider en partie le protocole de traitement des mesures.Dans le futur, ce protocole peut être appliqué sur des alliages métalliques. / The metal industry is requesting essential thermophysical properties for modeling and optimizing elaboration processes.Thermophysical properties of metals and metal alloys in liquid state are well known. These properties depend on the temperature and are difficult to measure especially at high temperature. In the liquid state, the metal is reactive and easily contaminated .In the 1980s, Egry developed an electromagnetic levitator TEMPUS developed an electromagnetic levitator TEMPUS to measure thermophysical properties of molten metals and alloys using a contactless technique under microgravity conditions. In space, the effects of electromagnetic stirring and deformation in molten samples are much lower than on Earth.The use of this space tool is expensive. In order to reduce the cost while maintaining or even improving the quality of measurements, we wanted to replace microgravity by a continuous magnetic field.The work in this thesis includes measuring the thermal properties of metals by electromagnetic method using a modulated calorimetry technique.The work has been divided in two parts:-The first consisted in the numerical simulation of space levitator TEMPUS and a terrestrial levitator AEXAM.The numerical simulation of space levitator TEMPUS aims to determine the effect of the superposition currents of different induction frequencies (heating currents and centering) on the hydrodynamic and thermal behavior of the drop. Calculation results showed that in some cases the centering current is likely to act on the measures and therefore it should be taking into account.The numerical simulation of terrestrial levitator AEXAM was destined to determine the vertical oscillation frequency of the drop, the power dissipated, the velocity fields developed inside and temperature. The drop takes the form of a pear and oscillates at a frequency of 7 Hz. The Joule power dissipated in the load is maximum on the lower part of the drop and decreases towards the interior of the drop vanishing at the center. Convection in the drop creates an electromagnetic stirring and homogenizing the temperature field.-The second part present the experiments performed using the levitator AEXAM placed in a horizontal continuous magnetic field for dampening the vertical oscillation and the turbulence produced by the effect of the electromagnetic stirring as it was mentioned in the calculations.This allowed us the implementation of a new protocol for measuring thermal properties in liquid metals.The protocol is a post processing program based on the temperature field variation resulting from unsteady joule power dissipation in the charge. An implemented identification function provides a mathematical model based on performed measurements. The use of a wide range of system frequencies was required to obtain a robust mathematical model. This was achieved by using pseudo-white noise perturbation at the generator inlet. The program has been validated successfully on solid matter by reverse determination of thermal conductivity and heat capacity.The preliminary studies under continuous magnetic field without modulation have mounted for a maximum initial weight of 3.5, we have less mass loss and improved measurement stability of the inductor current, as well as the reproductivity of the measurements.The protocol was validated successfully on the liquid charge using modulated perturbation under a continuous magnetic field of 1 Tesla. The obtained values of the heat capacity and thermal conductivity were comparable to the values given by the literature which partially validates the protocol.As a perspective, this protocol can be applied to a wide range of metal alloys.