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ItemThe role of the catalyst in the growth of one-dimensional nanostructures(Georgia Institute of Technology, 2009-11-10) Kirkham, MelanieQuasi one-dimensional (1D) nanostructures show great promise for many applications, including in solar cells, nanogenerators and chemical sensors, due to the high surface-to-volume ratio and unique properties of nanostructures. The growth of these nanostructures is commonly catalyzed by metal nanoparticles and generally attributed to the vapor-liquid-solid (VLS) mechanism. The purpose of this research is to better understand the role of the catalyst nanoparticles in the growth of 1D nanostructures, in order to allow improved control of the synthesis process. To this end, nanostructures were grown with a variety of compositions, including Au- and Sn-catalyzed ZnO, Au-catalyzed FexOy and Au-catalyzed Si nanostructures. The morphology of the nanostructures was characterized with electron microscopy, and the crystallographic orientation with X-ray texture analysis. The catalyst particles were further characterized with both in-situ and post-growth X-ray diffraction. The types of bonding in the source material and catalyst play a significant role in the diffusion path of the source material to the growth front and in the catalyst particle state during growth. Dissimilar bonding types in the source material and catalyst prevent bulk diffusion of the source material through the catalyst, thereby preventing eutectic melting of the catalyst. These results bring new insight into the catalyzed growth of 1D nanostructures and assist in the informed choice of appropriate catalyst materials, which may aid the utilization of 1D nanostructures in energy-related and other applications.
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Item1D nanowires: understanding growth and properties as steps toward biomedical and electrical application(Georgia Institute of Technology, 2008-07-01) Morber, Jenny RuthThis work details the synthesis and growth mechanisms of 1D magnetic and semiconducting nanostructures. Specifically, magnetic iron oxide and ZnS-SiO2 nanowires are examined. These materials are chosen due to their promise for biomedical and electronic applications and the perceived need to both create these structures as tools for these applications and to understand their formation processes so that they can be manufactured at a scale and efficiency suitable for commercialization. The current state and impact of nanotechnology is discussed through the lens of continuing technological advances and environmental factors, and the term is defined according to a specific set of criterion involving size, utility, and uniqueness. Details of synthesis and characterization of Fe3O4, ε-Fe2O3, and ZnS-SiO2 core-shell nanowires are presented. Observations regarding the growth of these structures are paired with additional experiments, simple simulations, and other literature to discuss the classical VLS growth process in general, and its applicability to these structures in particular. Finally, some exciting future applications are discussed, with details for initial experimental work presented in the appendix.
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ItemHydrothermal conversion of diatom frustules into barium titanate based replicas(Georgia Institute of Technology, 2007-07-10) Ernst, Eric MichaelNumerous organisms produce ornately detailed inorganic structures (often known as shells) with features on length scales from the nanoscale to the microscale. One organism, commonly referred to as a diatom, originates from algae and is found throughout the oceans on Earth. These diatoms possess skeletal structures, frustules, made from silicon dioxide. This chemical makeup limits the number of possible applications for which these structures can be used. Using a series of gas displacement reactions, these frustules can be converted to other useful materials, such as magnesium oxide and titanium dioxide, while maintaining the features of the frustule template. In the current research, silicon dioxide frustules were converted to titanium dioxide replicas using method previously devised by our group. The titanium dioxide replicas were subjected to a hydrothermal reaction by exposing the replicas to an aqueous basic solution containing barium hydroxide to form barium titanate and barium strontium titanate replicas. The effects of reaction temperature, time, and solution composition on extent of conversion were examined. The conventional method of converting titanium dioxide to barium titanate, using a convection heating oven, was compared with a microwave assisted heating method to study the advantages of using microwave heating over convection heating.
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ItemThe kinetics of incongruent reduction between sapphire and Mg-Al melts(Georgia Institute of Technology, 2006-04-03) Liu, YajunThe kinetics of incongruent reduction between sapphire and oxygen-controlled Mg-Al melts was studied by measuring spinel-layer thickness, sample-weight change and sample-thickness change as a function of time at various temperatures. To eliminate the crucible contamination caused by impurities in commercial MgO crucibles, self-made high-purity MgO crucibles were achieved by gelcasting method, which is an attractive ceramic-forming technique for making high-purity ceramic parts. The oxygen-controlled alloys were obtained by the three-phase-equilibrium experiments at various temperatures. To avoid MgO formation, the oxygen-controlled alloys prepared at relatively lower temperatures were used for incongruent reaction at relatively higher temperatures. That is to say, the oxygen-controlled alloys prepared at 900°C, 1000°C, and 1100°C were used for spinel formation at 1000°C, 1100°C, and 1200°C, respectively. The experiments were conducted in a vertical furnace, and sapphire wafers were hung vertically in high-purity MgO crucibles so that the natural convection induced by the density change in the melt could be investigated. Experimental results obtained at 1000°C, 1100°C, and 1200°C showed that the spinel layer thickness on two kinds of sapphire wafers, namely {0001} and , followed orientation-independent parabolic kinetics, indicating the diffusion in spinel was one of the rate-limiting steps. In addition, the spinel layer thickness was not a function of position. The results of sample-thickness- change measurements also indicated that the effect of natural convection could be neglected. XPS, XRD, and TEM were also employed to characterize some samples in this study. Based on a simple model where the diffusion in spinel was the only rate-limiting step, the governing partial differential equations for diffusion and fluid dynamics were solved by the finite element method. The calculated theoretical parabolic constants at various temperatures were compared with these experimental results, and a good agreement was obtained. Some preliminary studies were also made on the morphologies of spinel particles at the nucleation stage. It was found that the triangular {111} faces of spinel particles were parallel to the surface of {0001} sapphire substrate. The product shape was consistent with the tetrahedron composed of {111} faces. The morphology of spinel particles on a sapphire substrate was more complicated in that the triangular {111} faces of spinel had to be inclined at a certain angle to the substrate in order to maintain the orientation relationship.
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ItemPulsed Laser Deposition of Hydroxyapatite Thin Films(Georgia Institute of Technology, 2005-01-17) Johnson, ShevonPulsed laser deposition (PLD) was used to deposit hydroxyapatite (HA) thin films on various substrates, including silicon (100) and titanium (Ti-6Al-4V) alloy. Thin films of amorphous HA were deposited at room temperature and then annealed over a range of temperatures. The microstructure and composition of the films were determined using scanning electron microscopy (SEM), energy dispersive x-ray spectroscopy (EDS), and X-ray diffraction (XRD). The HA films were found to achieve total crystallinity at 350㮠The mechanical properties of the films were studied by means of nanoindentation and scratch adhesion testing. Crystalline and adherent HA thin films prepared using PLD and post deposition annealing have many potential medical and dental applications.