There is a current requirement for technologies that store heat for both domestic and industrial applications. Phase-change materials (PCMs) represent an important class of materials that offer potential for heat storage. Heat-storage systems are required to undergo multiple melt/freeze cycles without any change in melting-crystallisation point and heat output. Salt hydrates are attractive candidates on account of their high energy densities, but there are issues associated with potential crystallisation of lower-hydrates, long-term stability, and reliable nucleation. An extensive review of the PCMs in the literature, combined with an evaluation of commercially available PCMs led to the conclusion that many of the reported PCMs, lack at least one of the key requirements required for use as a heat-storage medium. The focus of this research was therefore to identify and characterise new PCM compositions with tailored properties. New PCM compositions based of sodium acetate trihydrate were developed, which showed improved properties through the use of selective polymers that retard the nucleation of undesirable anhydrous sodium acetate. Furthermore, the mechanism of nucleation of sodium acetate trihydrate by heterogeneous additives has been investigated using variable-temperature powder X-ray diffraction. This study showed that when anhydrous Na2HPO4 was introduced to molten sodium acetate trihydrate at 58°C the hydrogenphosphate salt is present as the dihydrate. On heating to temperatures in the range 75-90°C the dihydrate was observed to dehydrate to form anhydrous Na₂HPO4. This result explains the prior observation that the nucleator is deactivated on heating. The depression of melting point of sodium acetate trihydrate caused by the addition of lithium acetate dihydrate has also been investigated using differential scanning calorimetry and powder X-ray diffraction. It has been possible to tune the melting point of sodium acetate trihydrate thereby modifying its thermal properties. Studies of the nucleation of sodium thiosulfate pentahydrate, a potential PCM, led to the structural characterisation of six new hydrates using single crystal Xray diffraction. All of these hydrates can exist in samples with the pentahydrate composition at temperatures ranging from 20°C to 45°C. These hydrates are: α-Na₂S₂O₃·2H₂O, which formed during the melting of α-Na₂S₂O₃·5H₂O; two new pentahydrates, β-Na₂S₂O₃·5H₂O and γ-Na₂S₂O₃·5H₂O; Na₂S₂O₃·1.33 H₂O, β-Na₂S₂O₃·2H₂O and Na₂S₂O₃·3.67 H₂O, which formed during the melting of β- Na₂S₂O₃·5H₂O. Furthermore, new PCMs in the 75-90°C range were identified. The commercial impact and route to market of several of the PCMs are discussed in the final chapter.

Actuellement, la stratégie de la production d’énergie repose sur les 3 concepts d’économie, de régénération et d’écologie. La production de biodiesel s’insère dans cette thématique et fait objet de ce travail. Un suivi cinétique de nucléation-croissance est réalisé sur des nanoparticules monodisperses d’oxo-alcoxydes de zirconium (ZOA). Ces nanoparticules sont préparées par voie sol-gel dans un réacteur à T-micro-mélangeur avec deux flux turbulents de ZNP et c dans 1-propanol à 20°C. Les nanodépôts des nanoparticules de ZOA ont été réalisés sur des substrats en silice et comparés aux nanopoudres récupérées après l’induction du sol de ZOA. Les nanodépôts et les poudres subissent un séchage à 80°C puis une imprégnation humide dans une solution aqueuse de 0,25 mol.L⁻¹ de H₂SO₄. Nous obtenons ainsi les nanodépôts catalytiques après une calcination à des températures comprises entre 500 et 700°C sous O₂. Les techniques de BET, ATG-ATD, MET, DRIFT, analyse élémentaire et DRX sont déployées pour caractériser ces catalyseurs. Les cinétiques du processus d’estérification et de transestérification ont été étudiées en fonction des conditions de la préparartion des catalyseurs nanostructurés. Les nanodépôts catalytiques acides de ZrO₂-SO₄²⁻ possèdent une activité catalytique 50 fois plus élevée que celle des nanopoudres dans la réaction d’estérification de l’acide palmitique dans le méthanol à 65°C. Les nanodépôts calcinés à 580°C ont la meilleure stabilité vis à vis des essais de recyclage. L’activité catalytique des nanodépôts est aussi valable avec d’autres charges dont la composition est similaire à celle des huiles non-comestibles puis celle des déchets gras. / In this work, we have realized novel nanoparticulate catalysts ZrO₂-SO₄²⁻ for biofuel production. We have studied nucleation-growth kinetics of zirconium-oxo-alkoxy (ZOA) nanoparticles in the sol-gel process. The monodispersed nanoparticles of 3.6 nm diameter were realised in a sol-gel reactor with rapid (turbulent) micro-mixing of liquid solutions containing ZNP and H₂O in 1-propanol at 20°C. The nanocoatings were realised of stable colloids of ZOA nanoparticles on silica beads along with common powders obtained after precipitation of unstable colloids. The acid ZrO₂-SO₄²⁻" catalysts were prepared after drying at 80°C, wet impregnation in 0.25 mol.L⁻¹ aqueous solution of sulfuric acid and subsequent thermal treatment between 500 and 700°C and studied with BET, DTA-DSC, TEM, DRIFT, elemental analysis, DRX and other methods. The catalyst nanocoatings calcinated at 580°C showed strong activity in esterification reaction of palmitic acid in methanol at 65°C, which is about 50 times higher than that of nanopowders, and also possesses the highest stability towards recycling. Tha catalytic performance of catalytic nanocoatings was also confirmed on unedible and waste oils.

Criteria for grain boundary dislocation nucleation are developed. A bicrystal containing two grain boundaries is placed under varying triaxial stress states using molecular dynamics. The local resolved shear, normal, and co-slip stresses needed for grain boundary dislocation nucleation are found. A framework is developed to detect the slip system grain boundary dislocation nucleation occurs on. A survey of the different ways grain boundary dislocation nucleation occurs in the sample shows a single grain boundary can nucleate dislocations in a rich variety of ways. Using the nucleation system and resolved stress values, criteria for grain boundary dislocation nucleation on different slip systems are developed. The proposed form of nucleation criterion suggests the activation stress has a linear dependence one the resolved shear, normal, and co-slip stresses. A residual analysis largely validates the efficacy of the proposed linear model. We show that the nucleation slip system cannot be predicted by a maximum Schmid factor analysis due to the non-Schmid resolved normal and co-slip terms. We show that a system's global pressure generally fails to predict nucleation; a local stress in the grain being nucleated into should be used. Using the nucleation criteria for each slip system, a yield surface for dislocation nucleation is built for the grain boundary used in this work.

Hearing requires proper function of the auditory hair cell, which is critically dependent upon its actin-based cytoskeletal structure. Eleven point mutations in gamma (γ) nonmuscle actin have been identified as causing progressive autosomal dominant nonsyndromic hearing loss (DFNA20/26); however, exactly why these mutations lead to deafness is unclear. Organization, stability, and repair of the hair cell cytoskeleton are highly regulated by actin binding proteins (ABPs), and two of the mutations, K118M and K118N, are located near an area of the actin monomer believed to be important in actin-ABP interactions. A third mutation, D51N, is located in a region of the actin monomer believed to be important for polymerization dynamics and stability in filamentous actin. I therefore hypothesized that the K118M/N mutations cause hearing loss due to impaired regulation of the actin cytoskeleton within the hair cell, whereas the D51N mutation likely interferes with polymerization dynamics and actin filament stability or flexibility. The goal of my thesis was to investigate the effects of these three mutations, K118M, K118N, and D51N, on actin dynamics and regulation. I show in Chapter 2 that the K118M/N mutations differentially affect regulation of actin by the Arp2/3 complex, but also, surprisingly, that the K118N mutation accelerates polymerization dynamics. Chapter 3 details a continued investigation of the K118M/N mutations to ascertain their effects on actin structure and dynamics, particularly with regard to how they may affect polymerization. Chapter 4 provides both an in vivo and in vitro characterization of the D51N mutation, which revealed that not only does the mutation significantly accelerate actin polymerization, it also causes significant effects on yeast mitochondrial morphology and cytoskeletal regulation. The work detailed within this thesis provides new insight into how the K118M/N and D51N mutations affect actin structure and dynamics and how these effects could lead to deafness. More importantly, this work provides a strong foundation for many future studies, ranging from structural investigation of the K118N and D51N actins as F-actin mimics, to the potential role of mitochondria in actin-based disease.

The mechanisms linking deposits of insoluble fibrils of amyloid proteins to the debilitating neuronal cell death characteristic of neurodegenerative diseases remain enigmatic. Recent findings suggest that transiently formed intermediate aggregates, and not the prominent neuronal plaques, represent the principal toxic agent. Evaluating the neurotoxicity of intermediate aggregates, however, requires unambiguous characterization of all aggregate structures present, their relative distributions, and how they evolve in time. Hen-egg white lysozyme represents an attractive model for studying intermediate aggregate formation since it is an extensively characterized globular protein, and its human variants can lead to systemic amyloidosis. Combining in-situ dynamic light scattering (DLS) with atomic force microscopy (AFM), we have characterized the morphologies and growth kinetics of intermediate aggregates formed during lysozyme fibrillogenesis. Upon incubation at elevated temperatures, small uniform oligomers form with their numbers increasing for several hours. After a variable lag period protofibrils spontaneously nucleate. The heights and widths of protofibrils closely match those of oligomers. This match in physical dimensions, combined with the delayed onset of protofibril nucleation vs. the continuous formation of oligomers, suggest that protofibrils both nucleate and grow from oligomers. Protofibril morphologies and structures, visualized with AFM, are quite distinct from subsequently emerging mature fibrils. Overall, the evolution of aggregate morphologies during lysozyme fibrillogenesis follows a clear hierarchical pathway: amyloid monomers initially coalesce into oligomers of uniform size. Their steadily increasing numbers eventually induce nucleation and growth of protofibrils. Protofibrils, in turn, nucleate and grow via oligomer addition until they start to self-assemble into micron-sized double-stranded fibrils.

Diamond is widely known for its extraordinary properties, such as high thermal conductivity, energy bandgap and high material hardness and durability making it a very attractive material for microelectronic and mechanical applications. Synthetic diamonds produced by chemical vapor deposition (CVD) methods retain most of the properties of natural diamond. Within this class of material, nanocrystalline diamond (NCD) is being developed for microelectronic and microelectromechanical systems (MEMS) applications. During this research, intrinsic and doped NCD films were grown by the microwave plasma enhanced chemical vapor deposition (MPECVD) method using CH4/Ar/H2 gas mixture and CH4/Ar/N2 gas chemistries respectively. The first part of research focused on the growth and characterization of NCD films while the second part on the application of NCD as a structural material in MEMS device fabrication. The growth processes were optimized by evaluating the structural, mechanical and electrical properties. The nature of chemical bonding, namely the ratio of sp²:sp³ carbon content was estimated by Raman spectroscopy and near edge x-ray absorption fine structure (NEXAFS) techniques. The micro-structural properties were studied by x-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The mechanical properties of the pure NCD films were evaluated by nano-indentation. The electrical properties of the conductive films were studied by forming ohmic as well as schottky contacts. In second part of this study, both free-standing and membrane capped field emitter devices were fabricated by a silicon mold technique using nitrogen incorporated (i.e., doped) NCD films. The capped field emission devices act as a prototype vacuum microelectronic sensor. The field emission tests of both devices were conducted using a diode electrical device model. The turn-on field and the emission current of free-standing emitter devices was found to be approximately 0.8 V/µm and 20 µA, respectively, while the turn-on fields of capped devices increased by an order of magnitude. The emission current in the field emission sensor changed from 1 µA to 25 µA as the membrane was deflected from 280 µm to 50 µm from the emission tip, respectively.

This dissertation study describes the development of novel heteroepitaxial growth of 3C-SiC layers by chemical vapor deposition (CVD). It was hypothesized that chloride addition to the "traditional" propane-silane-hydrogen precursors system will enhance the deposition growth rate and improve the material quality via reduced defect density. Thermodynamic equilibrium calculations were performed to obtain a criterion for which chloride specie to select for experimentation. This included the chlorocarbons, chlorosilanes, and hydrogen chloride (HCl) chloride containing groups. This study revealed no difference in the most dominant species present in the equilibrium composition mixture between the groups considered. Therefore, HCl was the chloride specie selected to test the hypothesis. CVD computerized fluid dynamic simulations were developed to predict the velocity, temperature and concentration profiles along the reactor. These simulations were performed using COMSOL Multiphysics and results are presented. The development of a high-temperature (1300 °C -1390°C) 3C-SiC growth process resulted in deposition rates up to ~38 µm/h. This is the highest value reported in the literature to date for 3C-SiC heteroepitaxy. XRD FWHM values obtained varied from 220 to 1160 arcsec depending of the process growth rate or film thickness. These values are superior or comparable to those reported in the literature. It was concluded from this study that at high deposition temperatures HCl addition to the precursor chemistry had the most significant impact on the epitaxial layer growth rate. Low-temperature (1000-1250°C) 3C-SiC growth experiments evidenced that the highest deposition rate that could be attained was ~2.5 µm/h. The best quality layer achieved in this study had a FWHM of 278 arcsec; which is comparable to values reported in the literature and to films grown at higher deposition temperatures in this study. It was concluded from this work that at lower deposition temperatures the HCl addition was more beneficial for the film quality by enhancing the surface. Surface roughness values for films grown with HCl additive were 10 times lower than for films grown without HCl. Characterization of the epitaxial layers was carried out via Nomarski optical microscopy, FTIR, SEM, AFM, XRD and XPS.

Réussir à contrôler la morphologie et la taille de particules solides obtenues par précipitation est un enjeu industriel majeur. C’est notamment le cas dans l’industrie nucléaire pour le recyclage du combustible usé. Les caractéristiques des précipités sont liées aux conditions de mélange des phases liquides dans les procédés. Les corrélations entre les paramètres physiques des particules obtenues et les conditions hydrodynamiques n’ont pas été examinées jusqu’à présent. Dans cette étude, des systèmes expérimentaux originaux, basés sur la coalescence de deux gouttes, sont utilisés afin de mieux comprendre les liens entre hydrodynamique et réaction de précipitation. Deux configurations de gouttes aqueuses ont été investiguées, la première consiste en deux gouttes posées à fort angle de contact (>90°) dans l’huile, il s’agit d’un système modèle pour les gouttes en émulsion, la second configuration correspond à deux gouttes posées à faible angle de contact (>25°) dans l’air. Dans chaque cas, une espèce réactive est dissoute dans chaque goutte, à savoir de l’acide oxalique ou du nitrate de cérium dans la seconde. Lorsque les deux gouttes se touchent, elles peuvent éventuellement coalescer, alors les espèces chimiques se mélangent et réagissent pour produire un précipité d’oxalate de cérium. Les caractéristiques de ce précipité et ses effets sur l’hydrodynamique sont examinés en fonction du solvant utilisé. De plus, dans le cas des gouttes posées sur une surface de silice dans l’air, une différence de tension de surface entre deux gouttes crée un gradient qui génère un flux de Marangoni dirigé de la goutte de faible tension de surface au-dessus de la goutte de forte tension de surface. En jouant sur la différence de tension de surface entre les deux gouttes, et ainsi sur le flux de Marangoni, il est possible de modifier les conditions hydrodynamiques lors de la coalescence des gouttes. Des mélanges eau/diols ont été utilisés comme solvant afin de pouvoir modifier la différence de tension de surface entre les liquides des deux gouttes indépendamment de leur concentration en réactif. Les diols utilisés, le 1,2-propanediol et le 1,3-propanediol sont des isomères, ils sont la même densité, des viscosités semblables mais des tensions de surface différentes. En fixant la fraction volumique d’eau dans le solvant, et en jouant sur les fractions volumiques de chaque diols, il est possible de contrôler la tension de surface des mélanges sur une gamme de 10 mN/m pour une concentration en réactifs donnée, et en conservant la densité et viscosité des solvants. Trois régimes de précipitation ont été identifiés dans le cas de la coalescence de gouttes d’eau/diols/réactifs en fonction de l’excès oxalique. Les motifs de précipitation en découlant ont été imagés par microscopie optique et les différents précipités ont été caractérisés à l’aide de microscopie confocale, MEB, DRX et SAXS. Le régime intermédiaire présente des motifs périodiques surprenants. Ces motifs correspondent à des domaines nettement délimités d’oxalate de cérium de différentes morphologies, à savoir des aiguilles et des « microflowers ». L’obtention de tels motifs peut s’expliquer par un mécanisme de rétroaction entre convection, réaction et diffusion. / The size and morphology control of precipitated solid particles is a major economic issue for numerous industries. For instance, it is interesting for the nuclear industry, concerning the recovery of radioactive species from used nuclear fuel. The precipitates features, which are a key parameter from the post-precipitate processing, depend on the process local mixing conditions. So far, the relationship between precipitation features and hydrodynamic conditions have not been investigated. In this study, a new experimental configuration consisting of coalescing drops is set to investigate the link between reactive crystallization and hydrodynamics. Two configurations of aqueous drops are examined. The first one corresponds to high contact angle drops (>90°) in oil, as a model system for flowing drops, the second one correspond to sessile drops in air with low contact angle (<25°). In both cases, one reactive is dissolved in each drop, namely oxalic acid and cerium nitrate. When both drops get into contact, they may coalesce; the dissolved species mix and react to produce insoluble cerium oxalate. The precipitates features and effect on hydrodynamics are investigated depending on the solvent. In the case of sessile drops in air, the surface tension difference between the drops generates a gradient which induces a Marangoni flow from the low surface tension drop over the high surface tension drop. By setting the surface tension difference between the two drops and thus the Marangoni flow, the hydrodynamics conditions during the drop coalescence could be modified. Diols/water mixtures are used as solvent, in order to fix the surface tension difference between the liquids of both drops regardless from the reactant concentration. More precisely, the used diols, 1,2-propanediol and 1,3-propanediol, are isomer with identical density and close viscosity. By keeping the water volume fraction constant and playing with the 1,2-propanediol and 1,3-propanediol volume fractions of the solvents, the mixtures surface tensions differ up to 10 mN/m for identical/constant reactant concentration, density and viscosity.Three precipitation behaviors were identified for the coalescence of water/diols/recatants drops depending on the oxalic excess. The corresponding precipitates patterns are visualized by optical microscopy and the precipitates are characterized by confocal microscopy SEM, XRD and SAXS measurements. In the intermediate oxalic excess regime, formation of periodic patterns can be observed. These patterns consist in alternating cerium oxalate precipitates with distinct morphologies, namely needles and “microflowers”. Such periodic fringes can be explained by a feedback mechanism between convection, reaction and the diffusion.

O sistema soda-cal-sílica se destaca na ciência e tecnologia de vidros, pois encontra enorme gama de aplicações, desde os tradicionais vidros de janela até biomateriais. Mesmo assim, a cinética de transformação de fases e em particular a cinética de cristalização de vidros não é bem conhecida em diversas regiões de composições nesse sistema clássico, dentre elas a do binário combeíta-devitrita (Na2O.2CaO.3SiO2 &#8211; Na2O.3CaO.6SiO2). Neste trabalho, a cinética de cristalização de vidros de várias composições no sistema combeíta-devitrita foi investigada por técnicas de microscopia ótica. A partir da determinação experimental das taxas de nucleação e crescimento, e do time-lag para nucleação, as energias interfaciais sólido-líquido super-resfriado para núcleos de tamanho crítico foram estimadas, assim como as difusividades para cada vidro. As temperaturas de transição vítrea, do início (onset) do pico de cristalização, liquidus e de transformação polimórfica da combeíta foram determinadas por Calorimetria Exploratória Diferencial em função da composição do vidro matriz. A taxa de nucleação da combeíta (fase cristalina primária) foi estimada em função da temperatura pelo \"método do desenvolvimento\" ou método de Tamman, em que primeiro realiza-se um tratamento térmico de nucleação de cristais e depois um tratamento para o crescimento dos mesmos até um tamanho mensurável ao microscópio óptico, para vidros de composições 100, 75 e 66,7 % em mol de combeíta. Observou-se um decréscimo da taxa de nucleação com a variação da composição, à medida que a mesma se distancia da combeíta estequiométrica e aproxima-se da composição eutética, devido a mudanças termodinâmicas e cinéticas, tais como o aumento da energia interfacial sólido-vidro e a diminuição da cinética de difusão, respectivamente. Também observou-se a mudança de composição da combeíta cristalizada e do vidro residual através da variação das temperaturas de transformação polimórfica e de transição vítrea, respectivamente, determinadas por DSC. Os resultados obtidos sobre a cinética de cristalização de vidros não-estequiométricos são originais e relevantes para o projeto da microestrutura de novos materiais vitrocerâmicos. / The soda-lime-silica system excels in glass science and technology due its wide range of applications, from traditional window glass to biomaterials. Nevertheless, the kinetics of phase transformation and in particular the glasses crystallization kinetics is not well known in several regions of compositions in this classical system, among them the combeite-devitrite joint (Na2O.2CaO.3SiO2-Na2O.3CaO.6SiO2). In this work, the kinetics of glass crystallization of several compositions in the combeite-devitrite joint was investigated by optical microscopy techniques. From the experimental determination of nucleation and growth rates, and time-lag for nucleation, the solid-supercooled liquid interfacial energies for critical-sized nuclei were estimated as well as the diffusivity for each glass. The glass transition, onset of crystallization peak, liquidus and combeite polymorphic transformation temperatures were determined by Differential Scanning Calorimetry as a function of matrix glass composition. The nucleation rate of the combeite (primary crystalline phase) was estimated as a function of temperature by the \"development method\" or by the method of Tammann, in which first a heat treatment for nucleation of the crystals is performed and then a treatment for growth up to one measurable size by optical microscope, for glasses of compositions 100, 75 and 66.7% mol of combeite. A decrease was observed in the nucleation rate with the variation of the composition as it distances from the stoichiometric combeite and approaches the eutectic composition due to thermodynamic and kinetic changes, such as the increase of the solid-glass interfacial energy and the decrease in diffusion kinetics, respectively. The change in composition of crystallized combeite and residual glass was also observed by the change of the polymorphic transformation and glass transition temperatures, respectively, determined by DSC. The results obtained on the crystallization kinetics of non-stoichiometric glasses are original and relevant for the design of the microstructure of new glass-ceramic materials.

Thesis (M.S.)--State University of New York at Binghamton, Department of Physics, 2006. / Includes bibliographical references.