Geopolymers are a relatively new class of material that has many broad applications, including use as a substitute for Ordinary Portland Cement (OPC), use in soil stabilisation, fire resistant panels, refractory cements, and inorganic adhesives. The synthetic alkali aluminosilicate structure of geopolymer results in a highly versatile material that can be synthesised en masse, cost competitively and from a wide varietyof aluminosilicate bearing raw materials. / Despite the commercial promise and technical viability of the technology, the fundamental understanding of the chemical structure and characteristics of geopolymeric materials, and to some degree the academic rigor of some aspects of the science related to geopolymers, leave a lot to be desired. In particular, the understanding of the effects of Si/Al ratio and alkali cation type on the molecular structure of the binder, and how these relate to the microstructure and mechanical and thermal properties are poorly understood. / The thesis explores the structure and characteristics of a systematic multi-dimensional matrix of geopolymers derived from metakaolin, a relatively pure aluminosilicate source. The thesis addresses the determination of the core molecular structure of geopolymers by solid-state NMR spectroscopy, and how this is altered by the nominal Si/Al ratio and alkali cation type. The chemical ordering is observed to reduce with Si/Al ratio and with inclusion of potassium over sodium. Most significantly, the presence of Al-O-Al linkages is identified for the first time in specimens with Si/Al ratios close to unity, by the application of 17O NMR techniques on geopolymers. The role of molecular structure and gel chemistry of geopolymers is elucidated, and links are drawn to understand the development of the microstructure and physical properties of the material. The thermal evolution of geopolymeric gels derived from metakaolin is investigated in terms of physical and structural development when exposed to temperatures up to 1000°C. The response of geopolymers to heating is characterised into four regions regardless of the extent of shrinkage or crystallisation. Several critical material performance relationships exist that are related to both the microstructure and chemical composition. / The thesis presents an updated structural model of geopolymers to include new insights obtained from application of solid-state NMR techniques and thermal analysis. The improvements in structural understanding described in the thesis have the potential to affect all aspects of geopolymer science.

Masters Research - Master of Philosophy (Engineering) / Thermal conduction properties are of major concern for those metal/ceramic composite materials having applications in semiconductor devices and electronic packaging materials. A higher thermal conductivity to coefficient of thermal expansion ratio is an advantage for such materials employed in electronic devices due to the subjective high thermal loads. It is well known that the shape, size and distribution of the insulating phase have an effect on the overall thermal conductivity properties. But the details are lacking and well deserving of study. Metal/ceramic oxide interfaces are important in the strengthening mechanisms of dispersion strengthened materials. Accordingly, considerable attention has been given to recent investigations of oxygen diffusion characteristics and the bonding mechanisms at such interfaces. Susceptibility to oxidation can be studied by analysing several thicknesses of material. As an example, studying a thin film and a semi-infinite material subjected to a high oxygen partial pressure environment and a vacuum condition would help to determine the oxidation (in-diffusion) and de-oxidation (out-diffusion) processes respectively. Since metal/ceramic internal interfaces play a very important role in controlling the mechanical, thermal and electrical properties, it is timely to consider these diffusion processes for detailed study. In this Thesis, the two areas mentioned above were selected for detailed investigation. The Thesis also addresses the further development of a method for solving complex phenomenological diffusion problems. This method makes use of lattice-based random walks of virtual particles, directed according to the Monte Carlo method (the Lattice Monte Carlo method) which is then used to address various mass and thermal diffusion processes. Chapter 2 is concerned with using this method to determine the thermal conductivity of model composites. In that chapter, the Lattice Monte Carlo method is used to calculate the effective thermal conductivity of several models of a composite, where inclusions are arranged in square planar and cubic arrangements with periodic boundary conditions. Excellent agreement is found of the effective thermal conductivity with the century-old Maxwell-Garnett Equation. Chapter 3 is concerned with a phenomenological representation of oxygen diffusion and segregation in a model composite based on Ag/MgO. The Lattice Monte Carlo method is employed to address mass diffusion in this composite. Square and randomly distributed multiple inclusions were considered as shapes of the MgO inclusion phase. The time-dependence of oxygen concentration depth profiles and contour maps were determined. First, oxygen in-diffusion is considered from a constant surface source solely into the Ag metal matrix: oxygen depth profiles were in excellent agreement with exact results. Next, oxygen in-diffusion/segregation is simulated in the composite by permitting and restricting the mobility of oxygen in different scenarios involving the Ag-MgO interface. The (higher temperature) out-diffusion of oxygen from the composite was also simulated and corresponding results obtained for the oxygen depth profiles. In both cases, very good agreement was found between the results from the Lattice Monte Carlo method and analytical expressions.

Mémoire (M.Sc.A.)-- Université du Québec à Chicoutimi, 1992. / Résumé disponible sur Internet. CaQCU Bibliogr.: f. 158-160, 220-221. Document électronique également accessible en format PDF. CaQCU

Thesis (M. S.)--Mechanical Engineering, Georgia Institute of Technology, 2009. / Committee Chair: Sitaraman, Suresh; Committee Member: Peak, Russell; Committee Member: Ume, Charles

Thesis (Ph.D.) - Carleton University, 2007. / Includes bibliographical references (p. 249-266). Also available in electronic format on the Internet.

abstract: The challenging search for clean, reliable and environmentally friendly energy sources has fueled increased research in thermoelectric materials, which are capable of recovering waste heat. Among the state-of-the-art thermoelectric materials β-Zn4Sb3 is outstanding because of its ultra-low glass-like thermal conductivity. Attempts to explore ternary phases in the Zn-Sb-In system resulted in the discovery of the new intermetallic compounds, stable Zn5Sb4In2-δ (δ=0.15) and metastable Zn9Sb6In2. Millimeter-sized crystals were grown from molten metal fluxes, where indium metal was employed as a reactive flux medium.Zn5Sb4In2-δ and Zn9Sb6In2 crystallize in new structure types featuring complex framework and the presence of structural disorder (defects and split atomic positions). The structure and phase relations between ternary Zn5Sb4In2-δ, Zn9Sb6In2 and binary Zn4Sb3 are discussed. To establish and understand structure-property relationships, thermoelectric properties measurements were carried out. The measurements suggested that Zn5Sb4In2-δ and Zn9Sb6In2 are narrow band gap semiconductors, similar to β-Zn4Sb3. Also, the peculiar low thermal conductivity of Zn4Sb3 (1 W/mK) is preserved. In the investigated temperature range 10 to 350 K Zn5Sb4In2-δ displays higher thermoelectric figure of merits than Zn4Sb3, indicating a potential significance in thermoelectric applications. Finally, the glass-like thermal conductivities of binary and ternary antimonides with complex structures are compared and the mechanism behind their low thermal conductivities is briefly discussed. / Dissertation/Thesis / Ph.D. Chemistry 2011

Les alliages métalliques amorphes possèdent une structure désordonnée sansordre atomique local à longue distance contrairement aux alliages cristallins. Cettestructure leur confère des propriétés particulières, ouvrant la voie à de nombreusesapplications industrielles. En particulier, leur conductivité thermique est faiblecomparée aux autres matériaux métalliques du fait de l'absence de réseau cristallin.Ces alliages possèdent ainsi des propriétés isolantes permettant de minimiser lespertes thermiques par conduction. Ce travail de thèse porte d'une part sur lacompréhension des mécanismes intervenant dans la conductivité thermique desalliages métalliques amorphes, permettant d'identifier des compositions adaptées.Différentes méthodes d'optimisation des propriétés thermiques ont été étudiées etont permis de développer une composition optimisée à faible conductivité thermique.D'autre part, la capacité à être assemblé a été étudiée dans l'objectif d'intégrer ces alliages dans un dispositif industriel. Deux techniques d'assemblage ont étéconfrontées permettant de développer une solution à court et à long terme. Deuxbrevets protégeant l'utilisation de compositions avantageuses obtenus grâce auxrésultats de ce travail ont été déposés. Par ailleurs, des prototypes ont été réalisés en utilisant les procédés étudiés dans ce travail et présentent des performances augmentées par rapport à la solution actuelle. / Bulk metallic glasses possess an amorphous structure without any atomic longrange ordering unlike their crystalline counterparts. They exhibit particularproperties due to this amorphous structure, which is very promising for futureindustrial applications. In particular, their thermal conductivity is very low compared to other metallic materials due to the absence of crystalline lattice. Thus, these alloys show some insulating properties, leading to low heat losses. This PhD work focuses on understanding the mechanisms that occur in thermal conductivity of bulk metallic glasses in order to identify suitable compositions. Several optimization methods have been carried out to minimize the thermal properties and resulted in the development of an optimized composition showing low thermal conductivity. Secondly, their joining ability has been studied with the aim to implement these alloys in an industrial device. Two different joining techniques have been faced to provide a short and a long term solution. Eventually, two patents which protect the use of beneficial compositions developed in this work have been filed. Besides, prototypes have been produced using the two processes studied in this work and show enhanced performances compared to the current solution.

Le pergélisol est une composante majeure du système climatique terrestre. Avec le réchauffement du climat, la dégel du pergélisol profite à l'activité biochimique qui décompose davantage de matière organique dans les sols arctiques et la rejette dans l'atmosphère sous forme de gaz à effet de serre (CO2, CH4). Ce phénomène pourrait constituer une rétroaction climatique positive majeure. Prédire ces effets nécessite d'étudier l'évolution du régime thermique du pergélisol ainsi que des facteurs qui l'influencent. Le manteau neigeux, de par son pouvoir isolant, contrôle les échanges de chaleur entre le sol et l'atmosphère une grande partie de l'année. Le flux de chaleur à travers la neige dépend de la hauteur du manteau neigeux et de la conductivité thermique des couches de neige qui le constituent. Ces deux variables sont elles-même très dépendantes des conditions climatiques et de la présence de végétation. Nous réalisons ici le suivi des propriétés de la neige et du sol d'un site haut arctique de toundra herbacée (Île Bylot, 73N), et d'un site bas arctique à la frontière de la toundra arbustive et forestière (Umiujaq, 56N). Nous utilisons les données issues de stations de mesure automatiques complétées par des mesures manuelles. Une attention particulière est portée sur la conductivité thermique de la neige, car peu de données sont disponibles pour les régions arctiques. Le modèle numérique couplé ISBA-Crocus est ensuite utilisé pour simuler les propriétés de la neige et du sol des deux sites étudiés. Les résultats sont comparés aux mesures de terrain afin d'évaluer la capacité du modèle à simuler le régime thermique des sols arctiques.Nous avons pu caractériser les interactions atmosphère-neige-végétation qui façonnent la structure des manteaux neigeux arctiques. Le vent et la redistribution de neige qu'il induit sont des paramètres fondamentaux qui déterminent la hauteur et la conductivité thermique de la neige. Un couvert végétal haut et dense (arbustes, arbres) piège la neige soufflée et l'abrite du tassement éolien. De plus, la structure ligneuse des massifs arbustifs soutient la masse de neige et empêche son tassement. Cet abri procure à la neige une capacité d'isolation élevée qui retarde le gel du sol dès les premières accumulations. Le refroidissement atmosphérique se poursuivant, le manteau neigeux peu épais est soumis à un gradient thermique élevé qui provoque d'importants transferts de vapeur d'eau depuis le sol et les couches de neige basales, vers les couches supérieures et l'atmosphère. La croissance de givre de profondeur qui s'opère, favorisée à la fois par le gradient thermique élevé et la faible densité de la neige, aboutit à la formation de couches très isolantes en contact avec la surface du sol. Tant que le sol demeure relativement chaud, la croissance de givre de profondeur perdure. Finalement, des épisodes de fonte peuvent avoir lieu en automne durant la mise en place du manteau neigeux dans les régions arctiques. Le regel de la neige peut rapidement annuler ou même temporairement inverser l'effet isolant des interactions neige-végétation. Une surface de neige gelée ne subit pas l'effet du vent et empêche sa redistribution. La formation de croûtes de regel à forte conductivité thermique accélère le refroidissement du sol. Le manteau neigeux affecté par la fonte au début de l'hiver a donc une capacité d'isolation diminuée qui pourrait entraver le réchauffement des sols arctiques. Nos résultats de simulation montrent que ces différents effets ne sont pas correctement représentés dans les modèles de neige. Les erreurs dans les conductivités thermiques de la neige simulées sont particulièrement problématiques puisqu'elles interviennent lors de la période de gel du sol. Étant donné l'étendue des régions affectées par le pergélisol, ces erreurs sur la modélisation de la neige arctique pourraient significativement affecter les simulations climatiques et les projections de la hausse des températures globales. / Permafrost is a major component of the Earth climatic system. Global warming provokes the degradation of permafrost which favors biogeochemical activity in Arctic soils. The decomposition of organic matter increases and results in the release of high amounts of greenhouse gases (CO2 and CH4) to the atmosphere. By amplifying the greenhouse effect induced by human activities, this phenomenon may constitute one of the strongest positive feedbacks on global warming. Predicting these effects requires to study the evolution of the permafrost thermal regime and the factors governing it. The snowpack, because of its insulating effect, modulates the heat fluxes between permafrost and atmosphere most of the year. The snow insulating capacity depends on snow height and thermal conductivity. These two variables are highly dependent on climatic conditions and on the presence of vegetation. Here we monitor the snow and soil physical properties at a high Arctic site typical of herbaceous tundra (Bylot Island, 73°N), and at a low Arctic site situated at the limit between shrub and forest tundra (Umiujaq, 56°N). We use data from automatic measurement stations and manual measurements. A special attention is given to the snow thermal conductivity because very few data are available for Arctic regions. Results are interpreted in relation to vegetation type and atmospheric conditions. The numerical coupled model ISBA-Crocus is then used to simulate snow and soil properties at our sites. Results are compared to field data in order to evaluate the model capacity to accurately simulate the permafrost thermal regime.We managed to describe atmosphere-snow-vegetation interactions that shape the structure of Arctic snowpacks. Wind and the snow redistribution it induces are fundamental parameters governing snow height and thermal conductivity. A high vegetation cover (i.e. shrubs and forest) traps blowing snow and shields it from wind compaction. Vegetation growth thus favors the formation of an insulating snowpack which slows down or even prevents soil freezing. Furthermore, the shrubs woody structure supports the snow mass and prevents the resulting compaction of bottom snow layers. Thus sheltered, snow in shrubs develops a high insulating capacity which delays soil freezing. Continued atmospheric cooling increases the thermal gradient in the snow, maintaining large water vapor transfers from the soil and the snow basal layers to upper layers and atmosphere. The growth of depth hoar, enhanced by the large thermal gradient and the low snow density, results in the formation of highly insulating snow layers thus constituting a positive feedback loop between soil temperature and snow insulation. As long as the soil stays relatively warm, depth hoar growth persists. Finally, if warm spells occur in autumn, they can trigger the partial melting of the early snowpack which can cancel or temporarily reverse the insulating effect of snow-vegetation interactions. A frozen snow surface prevents snow drifting and its redistribution. The presence of highly conductive refrozen layers facilitates soil cooling and reduces the thermal gradient. An early snowpack affected by melting is thus less insulative which could hamper Arctic soil warming. Simulation results show that these different effects are not correctly represented in snow models. Errors in the estimated snow thermal conductivities are particularly problematic as they highly affect the simulation of soil freezing. Given the area of permafrost-affected regions, these errors on Arctic snow modelling could significantly impact climate simulations and the global warming projections.

Ce travail de thèse a pour objectif d'étudier et de mieux comprendre les relations structure-propriétés de céramiques transparentes Yb:CaF2 obtenues par voie humide, en particulier sur le plan des propriétés thermiques. Dans un premier temps nous présentons les atouts des céramiques transparentes Yb:CaF2 dans le cadre d'une application en laser de puissance. Le procédé de fabrication par voie humide des céramiques est ensuite décrit au cours d'une seconde partie. Les résultats d'analyses et caractérisations diverses ayant eu lieu à différentes étapes de la synthèse des céramiques sont présentés, menant à une optimisation du procédé de fabrication. Un troisième chapitre est ensuite consacré à une étude expérimentale des propriétés thermiques de nos céramiques, qui montre en particulier une grande similitude avec les propriétés des monocristaux. Cette étude est complétée par un volet de modélisation décrit dans un quatrième chapitre. Deux modèles prédictifs de conductivité thermique sont explorés et comparés, et permettent d'apporter une explication théorique aux tendances observées expérimentalement. L'hypothèse selon laquelle l'impact des joints de grains sur la diminution de la conductivité thermique est négligeable devant celui du dopage est notamment confirmée. Enfin, dans une cinquième et dernière partie, plusieurs pistes sont explorées afin d'apporter une explication à l'échauffement supérieur des céramiques par rapport aux monocristaux observé en conditions laser. / This PHD work is aiming at getting a better understanding of the structure-properties relationships of Yb:CaF2 transparent ceramics obtained with a wet-route fabrication process, with a special focus on thermal properties. At first, we introduce the assets of Yb:CaF2 transparent ceramics in the frame of high-power laser applications. The wet-route fabrication process is then described in a second chapter. The results of several analysis and characterizations performed along different steps of the ceramics synthesis are also presented, leading to an optimized fabrication process. The third chapter then focuses on an experimental study of the thermal properties of our ceramics, which shows in particular an important similarity with single crystals properties. This study is complemented with a modelization work described in chapter four. Two predictive models of thermal conductivity are investigated and compared. They bring a theoretical explanation to the tendencies experimentally observed. We thereby confirm the hypothesis according to which the grain boundaries impact on thermal conductivity is negligible with respect to that of the doping element introduction. Finally, in the fifth and last chapter, several hypothesis are investigated in order to bring an explanation to the ceramics overheating observed in laser conditions, which is superior to single crystals.

Este trabalho apresenta uma revisão de técnicas para medir propriedades térmicas de lmes, seguida de enfoque na termo-re etância transiente (TTR). Dentre as tecnologias existentes para medir propriedades térmicas, métodos ópticos são preferidos devido à sua natureza não-destrutiva, potencial de alta resolução temporal e espacial e calibração independente de contato físico. A implementação experimental deste método é apresentada, assim como a teoria da linha de transmissão utilizada para tratamento por Transformada de Laplace da equação de Fourier unidimensional do calor. Para facilitar o cálculo de invers ão desta Transformada, uma aproximação numérica, empregando o método Stehfest, foi usada. Experimentalmente, a evolução temporal da temperatura normalizada é mostrada para um lme de Au sobre Si e para lmes de Cu sobre substratos de vidro e Si, assim como foram utilizadas técnicas complementares de caracterização dos lmes (per lometria, elipsometria, microscopia de força atômica, eletrônica de varredura e de transmissão). Para o filme de ouro com espessura de 4:6µm, a teoria apresenta boa concordância com os resultados experimentais, já que o valor encontrado para a condutividade térmica do ouro está entre 230W/m.K e 280W/m.K, próximo e abaixo do valor da condutividade térmica do Au em volume (318W/m.K), indicando a validade do método implementado. Para lmes de cobre, porém, os resultados iniciais não apresentam a mesma concordância, e possíveis causas são discutidas. Futuramente, a TTR implementada poderá ser utilizada para determinação da condutividade térmica de lmes nos dielétricos ou semicondutores, e possivelmente na caracterização da componente transversal em filmes anisotrópicos. / This work presents a review of techniques to measure thermal properties off films, followed by a focused attention to the transient termo-re ectance (TTR). Amongst the existing technologies to measure thermal properties, optical methods are preferred due their nondestructive nature, high potential of spacial and temporal resolution, and independence from physical contact. The experimental implementation of this method is presented, as well as the theory of the transmission line theory used in the Laplace Transform treatment of the Fourier one-dimensional heat conduction equation. To facilitate the calculation of the Transform inversion, a numerical method, using the Stehfest method, was used. Experimentally, evolution of the normalized temperature is shown for a lm of Au on Si and for films of Cu on glass and Si substrates, whereas complementary techniques were used for film characterization (pro lometry, ellipsometry, atomic force microscopy, scanning and transmission eletron microscopy). For the Au film 4:6µm thick, the theory presents good agreement with the experimental results, and the value found for the thermal conductivity of the gold film is between 230W/m.K and 280W/m.K, near and below the bulk Au thermal conductivity (318W/m.K), indicating the validity of the method implementation. For Cu films, however, the initial results do not present the same agreement, and possible causes are discussed. In the future, the implemented TTR could be used for determination of the thermal conductivity of dielectric or semicondutors thin films, and possibly in the characterization of the transversal component in anisotropic films.