Model heterogeneous catalysts have been synthesized and studied to better understand how the surface structure of noble metal nanoparticles affects catalytic performance. In this project, monodisperse rhodium and platinum nanoparticles of controlled size and shape have been synthesized by solution phase polyol reduction, stabilized by polyvinylpyrrolidone (PVP). Model catalysts have been developed using these nanoparticles by two methods: synthesis of mesoporous silica (SBA-15) in the presence of nanoparticles (nanoparticle encapsulation, NE) to form a composite of metal nanoparticles supported on SBA-15 and by deposition of the particles onto a silicon wafer using Langmuir-Blodgett (LB) monolayer deposition. The particle shapes were analyzed by transmission electron microscopy (TEM) and high resolution TEM (HRTEM) and the sizes were determined by TEM, X-ray diffraction (XRD), and in the case of NE samples, room temperature H2 and CO adsorption isotherms. Catalytic studies were carried out in homebuilt gas-phase reactors. For the nanoparticles supported on SBA-15, the catalysts are in powder form and were studied using the homebuilt systems as plug-flow reactors. In the case of nanoparticles deposited on silicon wafers, the same systems were operated as batch reactors. This dissertation has focused on the synthesis, characterization, and reaction studies of model noble metal heterogeneous catalysts. …

The Department of Energy`s program for disposing of nuclear High-Level Waste (HLW) and transuranic (TRU) waste has been impeded by overwhelming political opposition fueled by public perceptions of actual risk. Analysis of these perceptions shows them to be deeply rooted in images of fear and dread that have been present since the discovery of radioactivity. The development and use of nuclear weapons linked these images to reality and the mishandling of radioactive waste from the nations military weapons facilities has contributed toward creating a state of distrust that cannot be erased quickly or easily. In addition, the analysis indicates that even the highly educated technical community is not well informed on the latest technology involved with nuclear HLW and TRU waste disposal. It is not surprising then, that the general public feels uncomfortable with DOE`s management plans for with nuclear HLW and TRU waste disposal. Postponing the permanent geologic repository and use of Monitored Retrievable Storage (MRS) would provide the time necessary for difficult social and political issues to be resolved. It would also allow time for the public to become better educated if DOE chooses to become proactive.

The research program reported here is focused on critical issues that represent conspicuous gaps in current understanding of rapid solidification, limiting our ability to predict and control microstructural evolution (i.e. morphological dynamics and microsegregation) at high undercooling, where conditions depart significantly from local equilibrium. More specifically, through careful application of phase-field modeling, using appropriate thin-interface and anti-trapping corrections and addressing important details such as transient effects and a velocity-dependent (i.e. adaptive) numerics, the current analysis provides a reasonable simulation-based picture of non-equilibrium solute partitioning and the corresponding oscillatory dynamics associated with single-phase rapid solidification and show that this method is a suitable means for a self-consistent simulation of transient behavior and operating point selection under rapid growth conditions. Moving beyond the limitations of conventional theoretical/analytical treatments of non-equilibrium solute partitioning, these results serve to substantiate recent experimental findings and analytical treatments for single-phase rapid solidification. The departure from the equilibrium solid concentration at the solid-liquid interface was often observed during rapid solidification, and the energetic associated non-equilibrium solute partitioning has been treated in detail, providing possible ranges of interface concentrations for a given growth condition. Use of these treatments for analytical description of specific single-phase dendritic and cellular operating point …

In the United States we generate greater than 500 million tons of toxic waste per year which pose a threat to human health and the environment. Some of the most toxic of these wastes are those that are radioactively contaminated. This thesis explores the need for permanent disposal facilities to isolate radioactive waste materials that are being stored temporarily, and therefore potentially unsafely, at generating facilities. Because of current controversies involving the interstate transfer of toxic waste, more states are restricting the flow of wastes into - their borders with the resultant outcome of requiring the management (storage and disposal) of wastes generated solely within a state`s boundary to remain there. The purpose of this project is to study nuclear waste storage issues and public perceptions of this important matter. Temporary storage at generating facilities is a cause for safety concerns and underscores, the need for the opening of permanent disposal sites. Political controversies and public concern are forcing states to look within their own borders to find solutions to this difficult problem. Permanent disposal or retrievable storage for radioactive waste may become a necessity in the near future in Colorado. Suitable areas that could support - a nuclear storage/disposal …

The magnetic flux structures in the intermediate state of bulk, pinning-free Type-I superconductors are studied using a high resolution magneto-optical imaging technique. Unlike most previous studies, this work focuses on the pattern formation of the coexisting normal and superconducting phases in the intermediate state. The influence of various parameters such as sample shape, structure defects (pinning) and applied current are discussed in relation to two distinct topologies: flux tubes (closed topology) and laminar (open topology). Imaging and magnetization measurements performed on samples of different shapes (cones, hemispheres and slabs), show that contrary to previous beliefs, the tubular structure is the equilibrium topology, but it is unstable toward defects and flux motion. Moreover, the application of current into a sample with the geometric barrier can replace an established laminar structure with flux tubes. At very high currents, however, there exists a laminar 'stripe pattern.' Quantitative analysis of the mean tube diameter is shown to be in good agreement with the prediction proposed by Goren and Tinkham. This is the first time that this model has been confirmed experimentally. Further research into the flux tube phase shows a direct correlation with the current loop model proposed in the 1990's by Goldstein, Jackson …

Surface sensitive synchrotron X-ray scattering studies were performed to obtain the distribution of monovalent ions next to a highly charged interface at room temperature. To control surface charge density, lipids, dihexadecyl hydrogen-phosphate (DHDP) and dimysteroyl phosphatidic acid (DMPA), were spread as monolayer materials at the air/water interface, containing CsI at various concentrations. Five decades in bulk concentrations (CsI) are investigated, demonstrating that the interfacial distribution is strongly dependent on bulk concentration. We show that this is due to the strong binding constant of hydronium H3O+ to the phosphate group, leading to proton-transfer back to the phosphate group and to a reduced surface charge. Using anomalous reflectivity off and at the L3 Cs+ resonance, we provide spatial counterion (Cs+) distributions next to the negatively charged interfaces. The experimental ion distributions are in excellent agreement with a renormalized surface charge Poisson-Boltzmann theory for monovalent ions without fitting parameters or additional assumptions. Energy Scans at four fixed momentum transfers under specular reflectivity conditions near the Cs+ L3 resonance were conducted on 10-3 M CsI with DHDP monolayer materials on the surface. The energy scans exhibit a periodic dependence on photon momentum transfer. The ion distributions obtained from the analysis are in excellent agreement …

Laser vibrometry is a technique used to detect vibrations on objects using the interference of coherent light with itself. Most vibrometry systems process only one target location at a time, but processing multiple locations simultaneously provides improved detection capabilities. Traditional laser vibrometry systems employ oversampling to sample the incoming modulated-light signal, however as the number of channels increases in these systems, certain issues arise such a higher computational cost, excessive heat, increased power requirements, and increased component cost. This thesis describes a novel approach to laser vibrometry that utilizes undersampling to control the undesirable issues associated with over-sampled systems. Undersampling allows for significantly less samples to represent the modulated-light signals, which offers several advantages in the overall system design. These advantages include an improvement in thermal efficiency, lower processing requirements, and a higher immunity to the relative intensity noise inherent in laser vibrometry applications. A unique feature of this implementation is the use of a parallel architecture to increase the overall system throughput. This parallelism is realized using a hierarchical multi-channel architecture based on off-the-shelf programmable logic devices (PLDs).

The ideal structural steel combines high strength with high fracture toughness. This dissertation discusses the toughening mechanism of the Fe/Co/Ni/Cr/Mo/C steel, AerMet 100, which has the highest toughness/strength combination among all commercial ultrahigh strength steels. The possibility of improving the toughness of this steel was examined by considering several relevant factors.

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The development of fast magic angle spinning (MAS) opened up an opportunity for the indirect detection of insensitive low-{gamma} nuclei (e.g., {sup 13}C and {sup 15}N) via the sensitive high-{gamma} nuclei (e.g., {sup 1}H and {sup 19}F) in solid-state NMR, with advanced sensitivity and resolution. In this thesis, new methodology utilizing fast MAS is presented, including through-bond indirectly detected heteronuclear correlation (HETCOR) spectroscopy, which is assisted by multiple RF pulse sequences for {sup 1}H-{sup 1}H homonuclear decoupling. Also presented is a simple new strategy for optimization of {sup 1}H-{sup 1}H homonuclear decoupling. As applications, various classes of materials, such as catalytic nanoscale materials, biomolecules, and organic complexes, are studied by combining indirect detection and other one-dimensional (1D) and two-dimensional (2D) NMR techniques. Indirectly detected through-bond HETCOR spectroscopy utilizing refocused INEPT (INEPTR) mixing was developed under fast MAS (Chapter 2). The time performance of this approach in {sup 1}H detected 2D {sup 1}H{l_brace}{sup 13}C{r_brace} spectra was significantly improved, by a factor of almost 10, compared to the traditional {sup 13}C detected experiments, as demonstrated by measuring naturally abundant organic-inorganic mesoporous hybrid materials. The through-bond scheme was demonstrated as a new analytical tool, which provides complementary structural information in solid-state systems in …

High temperature alloys are essential to many industries that require a stable material to perform in harsh oxidative environments. Many of these alloys are suited for specific applications such as jet engine turbine blades where most other materials would either melt or oxidize and crumble (1). These alloys must have a high melting temperature, excellent oxidation resistance, good creep resistance, and decent fracture toughness to be successfully used in such environments. The discovery of Ni based superalloys in the 1940s revolutionized the high temperature alloy industry and there has been continued development of these alloys since their advent (2). These materials are capable of operating in oxidative environments in the presence of combustion gases, water vapor and at temperatures around 1050 C. Demands for increased f uel efficiency, however, has highlighted the need for materials that can be used under similar atmospheres and at temperatures in excess of 1200 C. The current Ni based superalloys are restricted to lower temperatures due to the presence of a number of low melting phases that result in softening of the alloys above 1000 C. Therefore, recent research has been aimed at exploring and developing newer alloy systems that can meet the escalating requirements. …

A 'true' critical current density, j{sub c}, as opposite to commonly measured relaxed persistent (Bean) current, j{sub B}, was extracted from the Campbell penetration depth, {lambda}{sub c}(T,H) measured in single crystals of LiFeAs, and optimally electron-doped Ba(Fe{sub 0.954}Ni{sub 0.046}){sub 2}As{sub 2} (FeNi122). In LiFeAs, the effective pinning potential is nonparabolic, which follows from the magnetic field - dependent Labusch parameter {alpha}. At the equilibrium (upon field - cooling), {alpha}(H) is non-monotonic, but it is monotonic at a finite gradient of the vortex density. This behavior leads to a faster magnetic relaxation at the lower fields and provides a natural dynamic explanation for the fishtail (second peak) effect. We also find the evidence for strong pinning at the lower fields.The inferred field dependence of the pinning potential is consistent with the evolution from strong pinning, through collective pinning, and eventually to a disordered vortex lattice. The value of j{sub c}(2 K) {approx_equal} 1.22 x 10{sup 6} A/cm{sup 2} provide an upper estimate of the current carrying capability of LiFeAs. Overall, vortex behavior of almost isotropic, fully-gapped LiFeAs is very similar to highly anisotropic d-wave cuprate superconductors, the similarity that requires further studies in order to understand unconventional superconductivity in cuprates and …

In this dissertation we focus on the investigation of the pairing mechanism in the recently discovered high-temperature superconductor, iron pnictides. Due to the proximity to magnetic instability of the system, we considered short-range spin fluctuations as the major mediating source to induce superconductivity. Our calculation supports the magnetic fluctuations as a strong candidate that drives Cooper-pair formation in this material. We find the corresponding order parameter to be of the so-called ss-wave type and show its evolution with temperature as well as the capability of supporting high transition temperature up to several tens of Kelvin. On the other hand, our itinerant model calculation shows pronounced spin correlation at the observed antiferromagnetic ordering wave vector, indicating the underlying electronic structure in favor of antiferromagnetic state. Therefore, the electronic degrees of freedom could participate both in the magnetic and in the superconducting properties. Our work shows that the interplay between magnetism and superconductivity plays an important role to the understanding of the rich physics in this material. The magnetic-excitation spectrum carries important information on the nature of magnetism and the characteristics of superconductivity. We analyze the spin excitation spectrum in the normal and superconducting states of iron pnictides in the magnetic scenario. …

The nonlinear coupling of intense, monochromatic, electromagnetic radiation with plasma is considered in a number of special cases. The first part of the thesis serves as an introduction to three-wave interactions. A general formulation of the stimulated scattering of transverse waves by longitudinal modes in a warm, unmagnetized, uniform plasma is constructed. A general dispersion relation is derived that describes Raman and Brillouin scattering, modulational instability, and induced Thomson scattering. Raman scattering (the scattering of a photon into another photon and an electron plasma wave) is investigated as a possible plasma heating scheme. Analytic theory complemented by computer simulation is presented describing the nonlinear mode coupling of laser light with small and large amplitude, resonantly excited electron plasma waves. The simulated scattering of a coherent electromagnetic wave by low frequency density perturbations in homogeneous plasma is discussed. A composite picture of the linear dispersion relations for filamentation and Brillouin scattering is constructed. The absolute instability of Brillouin weak and strong coupling by analytic and numerical means is described. (auth)

Atmospheric iron (Fe) is thought to play an important role in cloudwater chemistry (e.g., S(IV) oxidation, oxidant production, etc.), and is also an important source of Fe to certain regions of the worlds oceans where Fe is believed to be a rate-limiting nutrient for primary productivity. This thesis focuses on understanding the chemistry, speciation and abundance of Fe in cloudwater and aerosol in the troposphere, through observations of Fe speciation in the cloudwater and aerosol samples collected over the continental United States and the Arabian Sea. Different chemical species of atmospheric Fe were measured in aerosol and cloudwater samples to help assess the role of Fe in cloudwater chemistry.

The work described in this report was carried out at a national laboratory of the Department of Energy, during the time that the author was engaged in a Department of Energy Industrial Hygiene Graduate Fellowship. The national laboratory had a respiratory protection program with approximately 50 employees participating. The program was in place to protect employees from over-exposure to airborne contaminants while engineering and work practice controls were being installed and implemented. It was also in place to protect workers in situations where engineering and work control practices were not feasible, such as during maintenance and repair work, as well as in situations where engineering and work practice controls were not enough to lower the exposure to or below the Permissible Exposure Limit (PEL) as set by the Occupational Safety and Health Association (OSHA) as an eight-hour time weighted average (TWA) or an excursion limit. Respirators were also used for emergencies by the emergency response team.