With excellent electrical, thermal and mechanical properties as well as large specific surface area, graphene has been applied in next-generation nano-electronics, gas sensors, transparent electrical conductors, thermally conductive materials, and superior energy capacitors etc. Convenient and productive preparation of graphene is thereby especially important and strongly desired for its manifold applications. Chemically developed functionalized graphene from graphene oxide (GO) has significantly high productivity and low cost, however, toxic chemical reduction agents (e.g. hydrazine hydrate) and raised temperature (400-1100°C) are usually necessary in GO reduction yet not preferred in current technologies. Here, microwaves (MW) are applied to reduce the amount of graphene oxide (GO) at a relatively low temperature (~165°C). Experimental results indicate that resurgence of interconnected graphene-like domains contributes to a low sheet resistance with a high optical transparency after MW reduction, indicating the very high efficiency of MW in GO's reduction. Moreover, graphene is usually recumbent on solid substrates, while vertically aligned graphene architecture on solid substrate is rarely available and less studied. For TIMs, electrodes of ultracapacitors, etc, efficient heat dissipation and electrical conductance in normal direction of solid surfaces is strongly desired. In addition, large-volume heat dissipation requires a joint contribution of a large number of graphene sheets. Graphene sheets must be aligned in a large scale array in order to meet the requirements for TIM application. Here, thermally conductive fuctionalized multilayer graphene sheets (fMGs) are efficiently aligned in a large scale by vacuum filtration method at room temperature, as evidenced by SEM images and polarized Raman spectroscopy. A remarkably strong anisotropy in properties of aligned fMGs is observed. Moreover, VA-fMG TIMs are prepared by constructing a three-dimensional vertically aligned functionalized multilayer graphene architecture between contact Silicon/Silicon surfaces with pure Indium as a metallic medium. Compared with their counterpart from recumbent A-fMGs, VA-fMG TIMs have significantly higher equivalent thermal conductivity and lower contact thermal resistance. Electrical and thermal conductivities of polymer composite are also greatly interested here. Previous researches indicated that filler loading, morphology of fillers, and chemical bonding across filler/polymer interfaces have significant influence on electrical/thermal conductivity of polymer composite. Therefore, the research also pays substantial attention to these issues. First, electrical resistivity of CPCs is highly sensitive on volume or weight ratio (filler loading) of conductive fillers in polymer matrix, especially when filler loading is close to percolation threshold (pc). Thermal oxidation aging usually can cause a significant weight loss of polymer matrix in a CPC system, resulting in a filler loading change which can be exhibited by a prompt alteration in electrical resistivity of CPCs. Here, the phenomena are applied as approach for in-situ monitoring thermal oxidation status of polymeric materials is developed based on an electrical sensors based on conductive polymeric composites (CPCs). The study developed a model for electrical resistivity of sensors from the CPCs as a function of aging time at constant aging temperature, which is in a good agreement with a Boltzmann-Sigmoidal equation. Based on the finding, the sensors show their capability of in-situ in-situ monitor and estimate aging status of polymeric components by a fast and convenient electrical resistance measurement. Second, interfacial issues related to these thermal conductive fillers are systemically studied. On the one hand, the study focuses on relationship between morphology of h-BN particles and thermal conductivity of their epoxy composites. It is found that spherical-agglomeration of h-BN particles can significantly enhance thermal conductivity of epoxy resin, compared with dispersed h-BN plates, by substantially reducing specific interfacial area between h-BN and epoxy resin. On the other hand, surface of high thermal conductive fillers such as SiC particles and MWNTs are successfully functionalized, which makes their surface reactive with bisphenol A diglycidyl ether and able to form chemical bonding between fillers and epoxy resin. By this means, thermal conductivity of polymer composites is found to be significantly enhanced compared with control samples, indicating the interfacial chemical bonding across interface between thermal conductive fillers and polymer matrix can promote heat dissipation in polymeric composites. The finding can benefit a development of high thermal conductive polymer composites by interfacial chemical bonding enhancement to meet the demanding requirements in current fine pitch and Cu/low k technology.

The search of materials relevant for thermoelectric and magnetocaloric applications, as well as materials that interact with light, is an important aspect of the materials science. Such materials can be used for solid-state power generation and refrigeration, as light sources, detectors, or controllers. Intermetallic clathrates have long been of interest for the materials science research. The promise these materials hold for useful applications ranges from thermoelectrics to photovoltaics and optoelectronics to potentially ultra-hard materials and magnetic cooling applications. Their unique physical properties are intimately related to their intriguing structural properties. Thus a fundamental understanding of the chemistry and physics of inorganic clathrates offers the possibility to assess their potential for use in the various applications mentioned above. In this work the selective, phase pure, single-crystal growth of AxSi46 and AySi136 (A = Na, K) intermetallic clathrates by the new vapor-phase intercalation method is presented. The approach appears promising for accessing regions of the equilibrium diagrams for Na-Si and K-Si clathrates that can be otherwise difficult to reach due to the greatly differing properties of the constituent elements. Physical properties of these materials were investigated in terms of single-crystal diffraction, electrical and thermal properties measurements. The synthesis and structural properties of single crystals of NaxSi136 are presented. A two-step synthetic approach was employed for the synthesis of NaxSi136 which also allowed for low temperature transport measurements of polycrystalline NaxSi136. The potential of the Eu8Ga16Ge30 type-I and VIII - EuO composites for magnetocaloric applications is discussed. The type-I clathrate - EuO composites hold promise for active magnetic refrigeration around 70 K.

We conduct a comprehensive and systematic study of the Fermi-Pasta-Ulam (FPU) model using both equilibrium and non-equilibrium molecular dynamics simulations, with the aim being to explain the cause of the anomalous energy-transport behaviour in the model. In the equilibrium scenario, our motivation stems from the lack of a complete understanding of the effects of initial conditions on the energy dissipation among Fourier modes. We also critically reconsider the ????probes' that had been widely used to quantitatively describe the types of energy sharing in a system, and then decide on a preferred choice to be used in our equilibrium study. We establish, from strong numerical evidence, that there exists a critical energy density of approximately 0:1, above which the energy dissipation among the modes becomes independent of initial conditions and system parameters, and that the full equipartition of mode energy is never attained in the FPU model. We report, for the first time, the violation of particle positions in the FPU model at high energies, where the particles are found to pass through one another. In the non-equilibrium scenario, we critically review the Nos???Se-Hoover algorithm thermostatting method largely used by other works, and identify its weaknesses. We also review some other alternative methods and decide on the most appropriate one to be implemented throughout our work. We confirm the divergence of the thermal conductivity of the FPU model as the chain length increases, and that kfpu [symbol] No.41, in agreement with other works. Our study further shows that there exists an upper limit of the anharmonicity in the FPU model, and that any attempt to increase the strength of this anharmonicity will not succeed. We also introduce elastic collisions into the original FPU model and find that the Modified model (FPUC) still exhibits anomalous thermal conductivity. We conclude that a one-dimensional FPU-type model with ????only' nearest-neighbour interaction, regardless of being soft or hard, does not exhibit a finite thermal conductivity as the system size increases, due to the non-chaotic nature of its microscopic dynamics, the origin of which we are unable to account for. Finally, we briefly outline possible research directions.

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.

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.