Recent studies indicate B4C nanopowder may provide additional advantages without loss of established properties. In this study, preliminary forms of graphite-coated B4C nanopowders on the order of 20-40 nm with various additives were sintered and analyzed. Methanol washing was performed on the powders to remove most of the B2O3 impurity usually present. XRD analysis of the powders verified the nanograined nature and, to some extent, the amount of amorphous material within the powders. A dilatometer furnace was used to track the dimensional changes during sintering, and densities of sintered samples were compared to green compact densities. The onset of sintering occurred at various temperatures depending on the dopant and its amount, most often occurring at higher temperatures than expected. This was likely due first to volatilization of residual B2O3 and then to the graphite coatings of the powders preventing direct B4C-B4C contact. Double-stage sintering, where sintering is either slowed, arrested or reversed and then re-accelerated, occurred in all but one sample. Samples with sintered densities greater than 93% theoretical density were hot isostatically pressed (HIP) with the expectation that the post-HIP density would be 100% theoretical density. Ultimately, post-HIP densities increased less than 2% compared to sintered densities.

Si-based anodes have recently received considerable attention for use in Li-ion batteries, due to their extremely high specific capacity - an order of magnitude beyond that offered by conventional graphite anode materials. However, during the lithiation process, Si-based anodes undergo extreme increases in volume, potentially by more than 300 %. The stresses produced within the electrode by these volume changes can damage the electrode binder, the active Si particles and the solid electrolyte interphase (SEI), causing the electrode to rapidly fail and lose capacity. These problems can be overcome by producing new anode materials incorporating both Si and C, which may offer a favorable combination of the best properties of both materials, and which can be designed with internal porosity, thereby buffering the high strains produced during battery charge and discharge with minimal overall volume changes. However, in order to develop useful anode materials, we must gain a thorough understanding of the structural, microstructural and chemical changes occurring within the electrode during the lithiation and delithiation process, and we must develop new processes for synthesizing composite anode particles which can survive the extreme strains produced during lithium intercalation of Si and exhibit no volume changes in spite of the volume changes in Si. In this work we have developed several novel synthesis processes for producing internally porous Si-C nanocomposite anode materials for Li-ion batteries. These nanocomposites possess excellent specific capacity, Coulombic efficiency, cycle lifetime, and rate capability. We have also investigated the influence of a range of different parameters on the electrochemical performance of these materials, including pore size and shape, carbon and silicon film thickness and microstructure, and binder chemistry.

The term Nanoceramics is well known in the ceramic field for at least two decades. In this project a detailed study was performed on the synthesis of α-alumina nanopowders. High solids content nanoalumina suspensions were prepared and used to form green bodies using both wet and dry forming routes. The green bodies were then sintered using both conventional single and two-step sintering approaches. Synthesis: Two different synthesis methods, viz. precipitation and hydrothermal treatment, were used to synthesize fine α-alumina powders from aluminium chloride, ammonia solution and TEAH (Tetraethyl ammonium hydroxide). XRD, TEM and FEG-SEM were used to characterise the powders produced. The presence of commercial α-alumina powder as seed particles did not affect the transformation to α-alumina phase during the hydrothermal treatment at 220˚C in either basic or acidic environments. The results obtained from the precipitation route showed that the combined effect of adding α-alumina seeds and surfactants to the precursor solution could lower the transformation temperature of α-alumina from about 1200˚C for unseeded samples to 800˚C, as well as reducing the level of agglomeration in the alumina powders. The difference in transformation temperature mainly resulted from the nucleation process by the α-alumina seeds, which enhanced the θ → α transformation kinetics. The lower level of agglomeration present in the final powders could be due to the surface modifying role of the surfactants preventing the particles from growing together during the synthesis process. By introducing a further high-temperature step for a very short duration (1 minute) to the low-temperature heat treatment route (800˚C/12 h), the unseeded sample with added surfactant transformed into pure α-alumina phase. The newly-added step was shown to be an in-situ seeding step, followed by a conventional nucleation and growth process. The best final powder was compared with a commercial α-alumina nanopowder. Processing of alumina ceramics: The effect of low-molecular weight ammonium dispersants including Dispex-A40, Darvan-C and Dolapix-CE64, on high solids content nanoalumina suspensions was investigated. The nanosuspension prepared using the most suitable dispersant, Dolapix-CE64, was slip cast into ~53% dense, very homogeneous green bodies. This nanosuspension was also spray freeze dried into crushable granules using Freon as a foaming agent. Green compacts with density of ~53.5% were then formed by dry pressing the 2 vol% Freon-added spray freeze dried granules at 40 MPa. Both slip cast and die pressed green bodies were sintered using conventional single-step and two-step routes followed by characterising the density and grain size measurement of final dense compacts. The results have been compared with that of a submicron alumina ceramic prepared using a commercial α-alumina suspension. Highly dense alumina with an average grain size of ~0.6 μm was fabricated by means of spark plasma sintering at 1200˚C. The application of 500 MPa allowed achieving almost fully dense alumina at temperature as low as 1200˚C for 30 minutes with no significant grain growth.

Le but de cette étude est de développer un modèle quantitatif pour l’interaction et la propagation des neutrons de faible énergie dans les milieux nanodispersés (en utilisant la nanopoudre de diamant comme exemple), qui prend en compte l’influence de la densité moyenne nanodispersée sur les processus de la propagation et la diffusion des neutrons à basse énergie, et les informations sur la structure d'une nanopoudre de diamant.L'urgence du problème à résoudre est due au manque d'informations sur la complétude des concepts des systèmes étudiés, sur les mécanismes d'interaction des neutrons de basse énergie avec les matériaux nanostructurés, sur les caractéristiques des propriétés de la structure des nanodispersés. médias, sur l'évolution des systèmes nanodispersés sous l'influence des rayonnements. Le développement du modèle quantitatif proposé est nécessaire pour l'évaluation qualitative et l'interprétation de diverses données expérimentales. L’élaboration d’un modèle quantitatif et de méthodes de calcul quantitatif de l’interaction et de la propagation des neutrons de faible énergie dans les milieux nanodispersés permettra d’interpréter des données expérimentales indépendantes dans le cadre de concepts unifiés et de réduire considérablement la quantité de paramètres empiriques. interprétation quantitative des résultats expérimentaux.L'auteur recommande d'utiliser le modèle quantitatif proposé et l'ensemble de programmes informatiques conçus pour les estimations qualitatives et quantitatives et l'interprétation de divers résultats expérimentaux, ainsi que pour des calculs quantitatifs préliminaires au stade de la planification de l'expérience.La thèse consiste en une introduction, quatre chapitres, une bibliographie et des conclusions.Le premier chapitre présente les résultats de la recherche sur le niveau de développement technique mondial actuel des nanotechnologies nucléaires. Il est à noter qu’à l’heure actuelle, les nanotechnologies nucléaires sont au stade de la recherche universitaire fondamentale et exploratoire, principalement axée sur l’extraction et l’accumulation de nouvelles connaissances.Le deuxième chapitre propose un modèle pour la propagation des neutrons à faible énergie dans un milieu nanodispersé. Une expression est obtenue pour l'équation de transfert de neutrons dans la forme de diffusion, c'est-à-dire l'équation de type Boltzmann. Les conditions aux limites sont analysées et établies pour l'équation du transfert de neutrons dans l'approximation de diffusion, en tenant compte des processus cohérents et incohérents d'interaction des neutrons avec le matériau. La méthode variationnelle permet une solution analytique de l'équation de transfert pour la fonction de distribution des neutrons dans l'approximation de la diffusion des neutrons aux petits angles par les nanoparticules dans la poudre. Les données expérimentales permettent de développer un modèle de nanopoudre de diamant à utiliser dans les calculs.Le troisième chapitre décrit la conception d'un algorithme de simulation numérique du transfert de neutrons dans une nanopoudre de diamant. Les calculs de modèle de la section efficace pour la diffusion élastique cohérente des neutrons par les nanoparticules sphériques sont effectués: 1) calculs quantiques précis par la méthode de la fonction de phase; 2) calculs dans l'approximation de Born. À titre de référence, nous décrivons brièvement des méthodes standard pour simuler des valeurs aléatoires d'angles de diffusion et des transformations de systèmes de coordonnées dans une méthode de Monte Carlo par ordinateur pour simuler la propagation des neutrons en nanopoudre.Le quatrième chapitre présente les résultats des calculs numériques effectués après le modèle quantitatif suggéré. Les résultats des calculs numériques sont analysés et comparés avec des données expérimentales. La comparaison montre un accord satisfaisant de calculs avec les données d'expériences indépendantes. / The aim of the present study is to develop a quantitative model for the interaction and propagation of low-energy neutrons in nanodispersed media (using the diamond nanopowder as an example), which takes into account the influence of the nanodispersed medium density on the processes of propagation and scattering of low-energy neutrons, and the information about the structure of a diamond nanopowder.The urgency of the problem being solved is due to the lack of information about the completeness of the concepts of the systems under study, about the mechanisms of interaction of low energy neutrons with nanostructured materials, about the features of the properties of the structure of nanodispersed media, about the evolution of nanodispersed systems under the influence of radiation. The development of the proposed quantitative model is necessary for qualitative evaluation and interpretation of various experimental data. The development of a quantitative model and methods for the quantitative calculation of the interaction and propagation of low-energy neutrons in nanodispersed media will allow to interpret independent experimental data within the frames of unified concepts, and will significantly reduce the amount of empirical parameters in the quantitative interpretation of experimental results.The author recommends using the proposed quantitative model and the designed set of computer programs for qualitative and quantitative estimates and interpretation of various experimental results, and for preliminary quantitative calculations at the stage of experiment planning.The thesis consists of an introduction, four chapters, a bibliography and conclusions.The first chapter presents the results of the research into the level of current global technical development of nuclear nanotechnologies. It is noted that at present, the nuclear nanotechnologies are at the stage of fundamental and exploratory academic research, predominantly focused on the extraction and accumulation of new knowledge.The second chapter suggests a model for the propagation of low-energy neutrons in a nanodispersed medium. An expression is obtained for the neutron transfer equation in the diffusion form, i.e. Boltzmann type equation. The boundary conditions are analyzed and established for the neutron transfer equation in the diffusion approximation, accounting for coherent and incoherent processes of neutron interaction with the material. The variational method enables an analytical solution of the transfer equation for the neutron distribution function in the approximation of small angle neutron scattering by nanoparticles in the powder. The experimental data allows to develop a model of diamond nanopowder, which is to be used in calculations.The third chapter describes the design of an algorithm for numerical simulation of neutron transfer in a diamond nanopowder. Model calculations of the cross section for elastic coherent scattering of neutrons by spherical nanoparticles are carried out: 1) precise quantum-mechanical calculations by the phase-function method; 2) calculations in the Born approximation. For reference, we briefly describe standard methods for simulating random values of scattering angles and transformations of coordinate systems in computer Monte Carlo method simulation of neutron propagation in nanopowder.The fourth chapter presents the results of numerical calculations carried out after the suggested quantitative model. The results of numerical calculations are analyzed and compared with experimental data. The comparison shows a satisfactory agreement of calculations with the data of independent experiments.

Nickel aluminate reduced in hydrogen for 3 h at 500ºC was studied for desulfurization of model fuel comprised of dodecane spiked with benzothiophene (300 ppmw S). The nanopowder adsorbent was synthesized using combustion chemical vapor condensation, which created nickel aluminate with a BET specific surface area of 57.8 m2/g and average particle size of 11.7 nm. The nickel aluminate adsorbent removed 23 µmol of sulfur gram at breakthrough (<15 ppmw S). Regeneration by further heat treatment in hydrogen or air recovered 25% and 40% of original capacity, respectively.

Titanium dioxide (TiO2), one of the basic ceramic materials, has found a variety of applications in industry and in our daily life. It has been shown that particle size reduction in this system, especially to nano regime, has the great potential to offer remarkable improvement in physical, mechanical, optical, biological and electrical properties. This thesis reports on the synthesis and characterization of the nanocrystalline TiO2 ceramic in details. The study selected a simple sol-gel synthesis process, which can be easily controlled and reproduced. Titanium tetraisopropoxide, isopropanol and deionized water were used as starting materials. By careful control of relative proportion of the precursor materials, the pH and peptization time, TiO2 nanopowder was obtained after calcination at 400oC. The powder was analyzed for its phases using X-ray powder diffraction (XRD) technique. Crystallite size, powder morphology and lattice fringes were determined using high-resolution transmission electron microscopy (HR-TEM). Differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA) were used to study the thermal properties. As-synthesized powder was uniaxially compacted and sintered at elevated temperature of 1100-1600oC to investigate the effects of sintering on nano powder particles, densification behavior, phase evolution and mechanical properties. Microstructure evolution as a function of sintering temperature was studied by scanning electron microscopy (SEM). The results showed that 400oC was an optimum calcination temperature for the as-synthesized TiO2 powder. It was high enough to achieve crystallization, and at the same time, helped minimize the thermal growth of the crystallites and maintain nanoscale features in the calcined powder. After calcination at 400oC (3 h), XRD results showed that the synthesized nano-TiO2 powder was mainly in single anatase phase. Crystallite size was first calculated through XRD, then confirmed by HR-TEM, and found to be around 5~10 nm. The lattice parameters of the nano-TiO2 powder corresponding to this calcination temperature were calculated as a=b=0.3853 nm, c=0.9581 nm, α=β=γ=90o through a Rietveld refinement technique, which were quite reasonable when comparing with the literature values. Considerable amount of rutile phase had already formed at 600oC, and the phase transformation from anatase to rutile fully completed at 800oC. The above rutilization process was clearly recorded from XRD data, and was in good corresponding to the DSC-TGA result, in which the broad exothermic peak continued until around 800oC. Results of the sintered TiO2 ceramics (1100oC-1600oC) showed that, the densification process continued with the increase in sintering temperature and the highest geometric bulk sintered density of 3.75 g/cm3 was achieved at 1600oC. The apparent porosity significantly decreased from 18.5% to 7.0% in this temperature range, the trend of which can be also clearly observed in SEM micrographs. The hardness of the TiO2 ceramics increased with the increase in sintering temperature and the maximum hardness of 471.8±30.3 HV was obtained at 1600oC. Compression strength increased until 1500oC and the maximum value of 364.1±10.7 MPa was achieved; after which a gradual decrease was observed. While sintering at ambient atmosphere in the temperature range of 1100oC-1600oC helped to improve the densification, the grain size also increased. As a result, though the sintered density at 1600oC was the highest, large and irregular-shaped grains formed at this temperature would lead to the decrease in the compression strength.

Целью работы является высокотемпературный синтез ультрадисперсной кислородо-дефицитной керамики оксида алюминия и исследование люминесцентных свойств полученных керамик при импульсном возбуждении пучком электронов. В результате высокотемпературного синтеза исследуемого объекта получена ультрадисперсная керамика оксида алюминия. Показано, что интенсивный синтез в восстановительной среде приводит к изменению массы и геометрических параметров вследствие термического травления образцов. Исследована пористость синтезируемых образцов и построены диаграммы распределения частиц по размерам. Обнаружен рост интенсивности катодолюминесценции F-центров керамик, синтезированных в восстановительной среде в присутствие углерода, с увеличением температуры и длительности изотермического нагрева. Полученные керамики являются перспективными для их применения в дозиметрии ионизирующих излучений и радиотехнике. Проведен анализ экологических рисков и соблюдения правил безопасности жизнедеятельности при экспериментальных исследованиях. / The goal of current paper is to synthesize an ultrafine oxygen-deficient aluminum oxide ceramic by high-temperature technique and to study its luminescent properties by pulsed cathodoluminescence (PCL). Ultra dispersive aluminum oxide ceramics were obtained after high-temperature synthesis. It was shown that an intensive synthesis in a reducing atmosphere causes mass and geometric parameters changes due to samples thermal etching. The porosity of synthesized samples and constructed particle size distribution diagram were investigated. The growth of ceramics samples F-centers cathodoluminescence intensity due to temperature increase and duration of isothermal heating were observed. Ones were synthesized in reducing ambient with carbon presence Obtained ceramics samples are promising material for application in dosimetry of ionizing radiation and radio engineering. Analysis of environmental risks and health and safety regulations in experimental environment was carried out.

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Freeze casting is a colloidal processing technique that shows great promise for development of nanostructured materials. A ceramic nanopowder is dispersed with a polymer in water, under carefully controlled pH. The suspension is cast into a suitable mold and frozen, then de-molded and exposed to a vacuum to sublimate and remove the water. Polymer adsorption and rheology were studied to optimize and characterize a colloidal suspension of a 38 nm Al2O3 powder. The dispersant, dispersant amount, pH and solids loading were examined to determine the best conditions for freeze casting. Based on adsorption and viscosity data, optimal conditions for freeze casting were found with Poly(acrylic acid) (PAA) dispersant, at 2.00 wt% (of Al2O3), pH of 9.5, and a solids loading of 40 vol%. Carbon nanotubes (CNTs) were added to that suspension in increments of 0.14, 0.28, 0.53, 1.30 and 2.60 vol%. The viscosity increased dramatically upon addition of 1.30 vol% CNTs. The colloidal CNT-Al2O3 suspension was successfully freeze cast and the microstructure showed a very smooth fracture surface. It was determined that upon resting, the suspension undergoes a physical change which must be completed to obtain advantageous microstructure. Freeze cast Al2O3 discs with and without CNTs were measured using a concentric ring test, with strengths on the order of one MPa. The freeze cast sample was successfully debinded, but the heating profile attempted was not effective in obtaining full density. / Master of Science