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ItemSimulation and modeling of the powder diffraction pattern from nanoparticles: studying the influence of surface strain(Georgia Institute of Technology, 2011-07-07) Beyerlein, Kenneth RoyAccurate statistical characterization of nanomaterials is crucial for their use in emerging technologies. This work investigates how different structural characteristics of metal nanoparticles influence the line profiles of the corresponding powder diffraction pattern. The effects of crystallite size, shape, lattice dynamics, and surface strain are all systematically studied in terms of their impact on the line profiles. The studied patterns are simulated from atomistic models of nanoparticles via the Debye function. This approach allows for the existing theories of diffraction to be tested, and extended, in an effort to improve the characterization of small crystallites. It also begins to allow for the incorporation of atomistic simulations into the field of diffraction. Molecular dynamics simulations are shown to be effective in generating realistic structural models and dynamics of an atomic system, and are then used to study the observed features in the powder diffraction pattern. Furthermore, the characterization of a sample of shape controlled Pt nanoparticles is carried out through the use of a developed Debye function analysis routine in an effort to determine the predominant particle shape. The results of this modeling are shown to be in good agreement with complementary characterization methods, like transmission electron microscopy and cyclic voltammetry.
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ItemCharacterization of open celled metal foams(Georgia Institute of Technology, 2011-01-26) Lin, Stephanie JanetOpen cell metal foams are a type of engineered material can be characterized by high porosity, high strength to weight ratio, tortuous flow paths and high surface area to volume ratio. It is the structure that gives the metal foams the characteristics that make them well suited for many application including heat exchangers. In this work, the structure of open celled metal foams is quantitatively characterized using an image analysis based method in order to predict the evaporative heat transfer of the metal foam using the fluid permeability. Several image processing algorithms were developed to quantitatively characterize the porosity, surface area per unit volume and the tortousity of metal foams from digital images of the cross sections of the material, and an expression was used to calculate the fluid permeability. An algorithm was developed to partion the pore space in the digital images so that individual cells within the structure could also be quantitatively characterized. Tools were also developed to predict the structure of open celled foam processed using the sacrificial template method by digitally constructing microstructures based the particle packing of the sacrificial templating material.
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ItemZnO nanocones and nanoplatelets: synthesis and characterization(Georgia Institute of Technology, 2010-08-12) Chang, YanlingNanowire structure plays an important role in the development of nanotechnology. However, further study shows that the shape of nanowires may not be the ideal morphology for some applications such as solar cells and sensors. Thus, the purpose of this thesis is to find a low cost and high yield approach to the synthesis of other morphologies of nanostructures in order to further improve the performance of these nanodevices. To this end, a chemical approach has been extended to the synthesis ZnO nanocones and platelets. With UV illumination, the synthesis of ZnO nanocones was achieved on GaN films on sapphire and gold films on silicon substrates. Both TEM and XRD results show that as-grown ZnO nanocones are single crystals. The formation of ZnO nanocones could be explained by the absorption process of photons. The UV light induced thermal gradient modifies the heat distribution as well as the reagent transport. The chemical reaction system is kinetically limited and results in ZnO nanocones. If the UV light is blocked, the ZnO nanowires result. In addition, the density of ZnO nanocones is higher than ZnO nanowires grown without UV illumination. By this chemical approach, ZnO platelets could also be obtained on GaN films deposited by PLD, whose c-axis is parallel to the surface of the substrate. The diameters and the thickness of the platelets depend on the quality and thickness of GaN film. TEM results illustrate that the obtained ZnO platelets are single crystals grown along the <0 1 1 0> direction within the {0 0 0 1} planes. Relative growth rates of various facets were altered by the presence of [1 0 0] textured GaN film. The suppression of the growth along c axis can also be achieved by citrate anions as a structure-directing agent to adsorb selectively on ZnO basal planes. Electrical measurement shows that the resistance of ZnO platelets is about 20-40 GΩ¸ and it is higher than that of ZnO nanowires. Piezoelectric potential calculation results also indicate that the piezoelectric potential is higher than for ZnO nanowires with the same external applied stress. These procedures and results demonstrate an easy and low cost way to fabricate ZnO nanocones and platelets, which may aid the utilization of nanostructures in solar cells, sensors and other applications to further improve their performance.
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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.