No description available.

Les alliages à mémoire de forme Nickel Titane sont des matériaux aux propriétés remarquablesdues à une transformation martensitique réversible et sont largement utiliséspar l’industrie biomédicale et dans des dispositifs de type actionneurs. La première partiede cette étude porte sur une analyse de leur comportement thermomécanique basée surla réalisation de mesures de champs cinématiques (par corrélation d’images visibles) etthermiques (par caméra infrarouge). Une part importante du travail présenté concernel’amélioration des calculs de sources de chaleur à partir des champs de température. Pource faire, les capacités et conductivités thermiques des phases austénitique et martensitiqueont été estimées par différentes méthodes expérimentales. Ensuite, la méthode de calcul desource a été validée sur des données virtuelles obtenues numériquement et sur des donnéesexpérimentales obtenues lors d’une transformation martensitique induite par un refroidissementnaturel. Cette première partie se conclut par l’application des développements àdes mesures réalisées lors d’un essai de cisaillement. La seconde partie est une contributionà la réalisation de matériaux architecturés constitués d’empilement de tubes de NiTi liésentre eux ; notre étude concerne la réalisation et la caractérisation de liaisons de tubes deNiTi par soudage résistif. / NiTi shape memory alloys have amazing properties due to a reversible martensitictransformation and are widely used by biomedical industries and as actuators. The firstpart of this study deals is a thermomechanical analysis of the material, based on kinematical(with digital image correlation) and thermal (with infrared camera) field measurements.An important part of this work deals with the improvement of the heat sources estimationfrom thermal fields. For this, thermal heat capacities and conductivities of austeniteand martensite were estimated with several experimental methods. Then, the heat sourceestimation method was validated from virtual data obtained numerically and from experimentaldata obtained during a martensitic transformation induced by natural cooling.This first part is concluded with the use of this technique to study shear tests. The secondpart of this study is a contribution to the realization of architectured materials composedof linked stacked tubes. Our study deals with the realization and the characterization ofthe NiTi link, realized by resistance welding.

Submitted by Renata Lopes (renatasil82@gmail.com) on 2017-11-07T12:20:00Z No. of bitstreams: 1 gessicalacerdasiqueira.pdf: 2914379 bytes, checksum: 13b701ceac7f6562db4c0a3167e60c32 (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2017-11-09T14:37:17Z (GMT) No. of bitstreams: 1 gessicalacerdasiqueira.pdf: 2914379 bytes, checksum: 13b701ceac7f6562db4c0a3167e60c32 (MD5) / Made available in DSpace on 2017-11-09T14:37:17Z (GMT). No. of bitstreams: 1 gessicalacerdasiqueira.pdf: 2914379 bytes, checksum: 13b701ceac7f6562db4c0a3167e60c32 (MD5) Previous issue date: 2017-07-13 / Processos de transferência de calor com mudança de fase são de interesse em várias áreas da ciência, engenharia e aplicações industriais. Em processos de solidificação, por exemplo, a ocorrência de trincas e formações de vazios causados por uma redução na capacidade de resistir a esforços mecânicos geralmente são observados, e é de grande importância prever esses comportamentos para que possam ser evitados. Uma das formas de se estudar esses fenômenos e suas aplicações é através do uso de modelos matemáticos que possibilitam, através do uso de métodos de discretização temporal e espacial a realização de simulações computacionais. Dessa forma, este trabalho estudou e comparou diferentes formulações numéricas do método dos elementos finitos para problemas de transferência de calor com mudança de fase levando em consideração a condução como mecanismo de transferência de calor. Na metodologia usada, os processos de solidificação ou fusão foram tratados por meio de métodos baseados em malhas fixas. Diversos experimentos numéricos foram realizados para se analisar a adequabilidade dos métodos estudados e propostos neste trabalho e os resultados obtidos foram satisfatórios. / Heat transfer processes with phase change are of great interest in several areas of science, engineering and industrial applications. In some of these applications, such as in solidification processes, the occurrence of cracks and void formation caused by a reduction in the ability of the material to resist mechanical loadings are generally observed, and it is of great importance to predict these behaviors so that they can be circumvented. One of the ways to study these phenomena and their applications is through the use of mathematical models and executing of computer simulations. Thus, this work studied and compared different numerical formulations of the finite element method for the heat transfer problems with phase change considering only conduction as the main mechanism of heat transfer. In the methodology used, the solidification or melting processes were treated by means of numerical methods based on fixed meshs. Several numerical experiments were performed to analyze the suitability of the methods studied and proposed in this work and the results were satisfactory.

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.

The project elaborated in frame of engineering studies is submitting the study of thermal properties of holding mixtures using different types of sand. Were tested a total of 5 sands: zirkon, ŠH22, chromite, olivine and dunite. Molding compounds were tested for thermal capacity, thermal conductivity and heat accumulation. The highest heat capacity was achieved in dunite sand. The largest heat accumulation had mixture with chromite sand and the best thermal conductivity was found in a mixture with olivine sand.

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.

Decisions made at the early stage of building design can significantly influence theenvironmental, energy and economic performance of buildings. Future homeowners anddevelopers often have to make decisions concerning the design and specification of thebuilding. These choices are usually governed by functionality, aesthetics, cost, materialavailability, etc. Except for decisions related to long-term performances, they are relativelyeasy and straightforward to make. Long-term performance assessments that consider theimpact of a product over its lifetime, requires thorough research. Due to the lack of studies onthe long-term benefits and performance of different building design options, homeowners anddevelopers often base their decisions on short-term financial benefits, ignoring long-termbenefits. This may lead to incorrect decisions that are difficult to correct.Within this context, the aim of this study is to compare the long-term economic viability ofdifferent external timber wall construction types. By doing so, our goal is to address the lackof techno-economic studies within the construction industry and thus, to assist the decisionmakingof Swedish homeowners and developers. We evaluate the economic performance ofthree wooden wall construction alternatives—that of IsoTimber, cross-laminated timber(CLT), and timber frame walls—via thirteen wall assembly scenarios and two case housesfrom Bysjöstrand eco-village, Sweden. The scenarios account for variations in wall type andwall thicknesses. Our study utilizes an approach based on life cycle costing (LCC) andconsiders the capital cost and the present value of heating cost. The latter is calculated for 1m2of heated area of each case houses over a 40-year period. Indoor Climate and Energy software(IDA ICE) is used to estimate the heating energy use and the Bidcon program to estimate thematerials and labor costs for all cases. The study considered reasonable economic parameters,but to see their impact on the results and feasibility of wall constructions improving, sensitiveanalysis has been done using different values.The main finding of this thesis is that timber frame wall construction is the most economicchoice in the long term. In contrast, IsoTimber wall is the least economic choice, in general,and for two-story homes, in particular. Moreover, the present value total cost for IsoTimber intwo-story building is 5% higher than for a single-story building that has a similar U-value. Incontrast, it is 3% and 7% lower for CLT and timber frame walls respectively. Also, the resultsindicate that although the present value heating cost decreases with increasing wall thickness,this increase is considerably smaller than the increase in the capital cost. Finally, assumedeconomic factors affect the results greatly, but in general, improving the U-value of CLT wallconstruction might be the most profitable then timber frame comes after, and then IsoTimbercomes in the last. Along with, return economic benefit from the improvement of all studiedwall constructions in single-story building is higher than the benefit in two-story building.

Lithiumeisen(II)-phosphat ist ein vielversprechendes und umweltfreundliches Kathodenmaterial für den Einsatz in Lithium-Ionen-Batterien (LIB), das eingehend im Hinblick auf seine thermodynamischen- und Oberflächeneigenschaften untersucht wurde. Zur Bestimmung der mittleren molaren Mischungsenthalpie von LiFePO4 und FePO4 wurde die Methode der isothermen Titrationskalorimetrie für die Untersuchung heterogener Stoffsysteme optimiert. Die Ergebnisse konnten mit elektrochemischen Gleichgewichtszellspannungsmessungen validiert werden. Ferner wurde die Oberflächenspannung von reinem LiFePO4 experimentell mit Hilfe der Kapillar-Aufstiegsmethode an Pulvern ermittelt. Ein weiterer Forschungsschwerpunkt stellte experimentelle Bestimmung der Wärmekapazität von phasenreinem orthorhombischen FePO4 dar. Des Weiteren wurde der Ablauf der hydrothermalen LiFePO4-Synthese ausgehend von Li3PO4 und Vivianit anhand von in-situ Messungen der elektrolytischen Leitfähigkeit und thermodynamischen Modellierungen aufgeklärt.

There is growing demand for a more efficient use of polymers that originate from renewable feedstocks due to the depleting supply of fossil fuels, based on economic and environmental reasons. As a result, lignin has attracted renewed interest as a resource for various bioproducts. Lignin is a natural biopolymer with a high carbon content and is composed of aromatic moieties, with a high level of polar functionalities. This makes it a unique precursor for certain high-value applications, such as in biofuels, bioplastics, composite materials, carbon fibers and activated carbons and as a source of phenolic monomers and fine chemicals. Industrial lignins are formed as byproducts of pulping processes (such as kraft, sulfite or alkaline pulping) or result from the biorefining process, where carbohydrates are used for sugar production. Lignin’s intrinsic structure is significantly modified during the processing of lignocellulose, resulting in the formation of more diverse, condensed and less reactive raw materials. Since molecular mass and polydispersity are the most important parameters affecting the chemical reactivity and thermal properties of lignin, additional process steps to improve the quality of crude technical lignins, including kraft lignin, are needed. Solvent extraction is a potentially useful technique for further improving the polydispersity of technical lignins. This work summarizes the impact of solvent fractionation on the chemical structure, antioxidant activity, heating value, and thermal and sorption properties of industrial hardwood and softwood kraft lignins. The purpose was to understand the correlation between certain structural features in the lignin fractions and their properties to select the appropriate solvent combinations for specific applications of lignin raw materials. Four common industrial solvents, namely, ethyl acetate, ethanol, methanol and acetone, in various combinations were used to separate both spruce and eucalyptus kraft lignins into fractions with lower polydispersities. Gel-permeation chromatography analysis was used to evaluate the efficiency of the chosen solvent combination for lignin fractionation. The composition and structure of the lignin material were characterized by elemental analysis, analytical pyrolysis (Py-GC/MS/FID) and 31P NMR spectroscopy. The thermal properties of the lignin samples were studied by thermogravimetric analysis. Proximate analysis data (ash, volatile components, organic matter and fixed carbon) were obtained through the direct measurement of weight changes during the analysis, while the high heating values (in MJ/kg) were calculated according to equations suggested in the literature. The sorption properties of fractionated kraft lignins were studied with respect to methylene blue dye. Additionally, lignin fractions with different molecular weights (and therefore various chemical structures) that were isolated from both softwood and hardwood kraft lignins were incorporated into a tunicate cellulose nanofiber (CNF)-starch mixture to prepare 100% bio-based composite films. The aim was to investigate the correlation between lignin diversity and film performance. The transmittance, density and thermal properties of the films were investigated, as were their mechanical properties, including the tensile stress and Young’s modulus. This part of the study addressed the importance of lignin diversity on composite film performance, which could be helpful for tailoring lignin applications in bio-based composite materials based on the material’s specific requirements.

Im Mittelpunkt der Arbeit stehen Alanate und Aluminiumhydride der Übergangs- und Erdalkalimetalle in Bezug auf ihre Synthese, ihre thermodynamischen Eigenschaften, ihre Zersetzungsreaktionen und ihre potentielle Eignung für reversible Wasserstoffspeicheranwendungen. Es konnten für CeAlH6, Mg(AlH4)2, Ca(AlH4)2, Sr(AlH4)2, CaAlH5 und SrAlH5 die Wärmekapazitätsfunktionen sowie die absoluten Entropien und Bildungsenthalpien bei 298,15 K bestimmt werden. Weiterhin wurden Methoden zur Näherung der genannten thermodynamischen Daten evaluiert und mit den ermittelten Werten aktualisiert und erweitert. Außerdem wurde die im Bereich der komplexen Hydride übliche Annahme, dass sich die bei der Synthese gebildeten Nebenprodukte LiCl und NaCl gegenüber den Hydriden inert verhalten, überprüft. Es konnte gezeigt werden, dass die Annahme hinsichtlich der Eigenschaften und Zersetzungsreaktionen von Mg(AlH4)2, Ca(AlH4)2 und Sr(AlH4)2 Bestand hat. In Bezug auf die Dehydrierung von CaAlH5 und SrAlH5 ist sie jedoch ungültig, wenn die Probe LiCl enthält.