A systematic method was developed for the deposition of β-SiC thin films on Si(100) substrates in a hot wall reactor, using low pressure chemical vapor deposition (LPCVD). Due to poor adhesion resulting from lattice mismatch and difference in thermal expansion coefficients between the (SiC films and the Si(100) substrates, the feasibility of forming a SiC buffer layer on the Si(100) surface before beginning the chemical vapor deposition (CVD) process was investigated. The SiC buffer layers were formed with either a smooth or porous morphology. A nonporous Si(100) substrate with a 35Å thick SiC buffer layer was formed when the Si surface was heated at 1050°C in an atmosphere of C₂H₂ and H₂. A porous surface was obtained when the Si substrate was heated at 1000°C in C₂H₂ alone. The porous defects were correlated to the out—diffusion of Si in the carburizing process. On smooth Si(100) substrates, polycrystalline and stoichiometric β-SiC thin films with the (111) planes paralleling the Si(100) substrates were grown from a CH₃SiCl₃ (MTS)—H₂ mixture at 1050°C. At high H₂/MTS ratios and/or low deposition pressures, no etching on the Si substrates of the β-SiC films was observed, resulting in a smooth topography. Degradation in film morphology, changes in the preferred orientation, and etching of the Si substrates were observed at higher pressures, temperatures, and H₂/MTS ratios. The etching of the Si substrate was due to the out—diffusion of Si atoms from the substrate and the presence of Cl—containing radicals, which resulted from the decomposition of MTS molecules before arriving at the substrates. A model of the deposition mechanism is proposed which predicts the deposition rates in a hot wall CVD reactor and agrees very well with the experimental data. On the Si(100) substrate with a porous topography, epitaxial β-SiC(100) thin films were grown from MTS—H₂ at 1150°C. The crystallinity of the deposited films was influenced by the deposition time. With increasing deposition time, rotational β-SiC(100) crystals and polycrystalline β-SiC with a highly preferred orientation of (100) and/or (111) were obtained. At a lower temperature of 1100°C, poor morphology and polycrystalline β-SiC thin films were observed. Finally, a new approach to the calculation of the local equilibrium CVD phase diagrams, which represent the most stable phases above the substrates in a hot wall reactor, for SiC deposition from the MTS—H₂ gas mixture by coupling the depletion effects to the equilibrium thermodynamic computer code SOLGASMIX—PV. The calculated CVD phase diagrams were also compared with experimental and the literature data. Although the local equilibrium CVD phase diagrams predicted the deposition of single phase SiC better than established CVD phase diagrams, the experimental regions for depositing single phase SiC are larger than those calculated from local CVD phase diagrams. This may be because of the high linear velocity of the gas flux under low pressure and the polarity of the Si—containing intermediate species. / Ph. D.

Pyrite (FeS₂) is the major source of sulfur in various coals, and its efficient removal has proven to be a more difficult task than expected. Flotation is generally considered to be the most practicable process for the preparation of coal fines. However, even this technique is usually unable to remove more than 50% of pyrite from a 65-mesh coal sample, which is the typical feed to flotation. There are three major reasons for the low separation efficiency of liberated pyrite from coal by flotation. They include self-induced hydrophobicity of pyrite caused by superficial oxidation, nonselective hydraulic entrainment of pyrite particles into froth product, and incomplete liberation of pyrite from coal that results in composite coal-pyrite particles, i.e., middlings. The present study was undertaken to address problems associated with these recovery mechanisms of pyrite and develop techniques to enhance pyrite rejection in coal flotation. To better understand self-induced hydrophobicity of pyrite, chronoamperometry and voltammetry on freshly fractured electrodes were used to explore incipient oxidation and reduction of the mineral. Voltammetry on rotating ring-disc electrodes (RRDE) was carried out to provide information on soluble species and kinetics of oxidation and reduction processes. X-ray photoelectron spectroscopy (XPS) was used for chemical identification of oxidation products. Galvanic coupling with sacrificial anodes was investigated as a practical method to cathodically protect pyrite and prevent its oxidation. Microflotation tests were conducted under controlled potentials at different solution pH's, and the results were correlated with electrochemical studies. The feasibility of improving pyrite rejection by controlling its surface chemistry was tested in flotation experiments conducted with a 2"-diameter microbubble flotation column and a conventional 5-liter Denver flotation cell. Effects of froth stability on the microbubble flotation of coal were studied with an objective of minimizing hydraulic entrainment of pyrite. The operating parameters were systematically varied to study their effects on water recovery which was used as a measure of froth stability. It has been demonstrated that the upgrading of coal in a flotation column can be significantly improved when froth stability is properly controlled. In an attempt to enhance the rejection of pyrite in middlings, various column circuits were experimentally examined and theoretically analyzed. The effect of circuit configuration on the overall circuit performance was evaluated by separation efficiency and separation curves. It has been shown that the overall separation efficiency of column flotation is rather insensitive to circuitry due to the unique characteristics of the unit flotation column, i.e., the addition of the wash water into the froth. / Ph. D.

The relative performance evaluation of the different alternatives of bridge topologies with zero-voltage switching is presented. A design-oriented analysis is developed to optimize implementation of the converters in terms of efficiency. Efficiency optimization requires minimizing the circulating currents which are directly proportional to the reactive energy required by the resonant tank. The comparison of the different converters is based on the reactive energy required for ZVS. The study considers resonant converters with conventional variable frequency control and with phase-shift control, and the zerovoltage- switched full-bridge PWM converter (ZVS-FB-PWM). Also, a systematic procedure to determine all possible resonant converters with two or three reactive elements is presented, and the design-oriented analysis used to classifY them according to their properties. The analysis for the resonant converters uses the fundamental approximation which is verified by comparison with the existing exact analysis for the series resonant converter (SRC), the parallel resonant converter (pRe) and the LCC resonant converter (LCC-RC). Comparison of design examples shows a superior performance for the LCC-RC, and less circulating current for the conventional variable-frequency resonant converters than for the phase-shifted control version. Experimental verification is provided for the phase-shifted resonant converters. The effect of switch capacitance on the zero-voltage switching (ZVS) of resonant converters is studied for the SRC, PRC and LCC-RC. The effect of switch capacitance is more' pronounced for low Q designs. Consequently, it is of primary importance for the LCC-RC whose optimal design requires low Q values. The results have been verified experimentally in an LCC-RC prototype. A complete analysis and design procedure are provided for the new ZVS-FB-PWM converter, including a new active clamp circuit that completely eliminates the ringing in the I rectifiers. The design procedure and design considerations have been verified with three' experimental prototypes. The comparison of the resonant converters with the ZVS-FB-PWM converter based on the reactive power required for ZVS, shows that the ZVS-FB-PWM converter is a superior alternative to resonant converters. The ZVS-FB-PWM converter always has less circulating current than the resonant converters when it is designed for a limited ZVS range. / Ph. D.

Three aspects of precipitate growth by a ledge mechanism in a Ni-45wt%Cr alloy were investigated. The strain energy for ledge formation and ledge growth kinetics and the emission of structural defects were studied experimentally during the growth of bcc laths from an fcc matrix. The elastic strain energy of a growth ledge as a function of the ledge location was estimated using an Eshelby-type model. Ledge nucleation is only likely at facet areas where the interaction energy between the ledge and the precipitate is negative. Ledges form with the lowest strain energy on the broad habit plane of coherent precipitates. On a partially coherent lath the strain energy is lowest for a ledge located on the facet perpendicular to the crystallographic invariant line. This situation favors precipitate lengthening in the invariant line direction. Experimental measurement of growth kinetics of the precipitate was made to examine the mechanistic relationship between precipitate growth kinetics and its morphology. TEM was employed to measure overall precipitate growth kinetics as function of time, crystallographic orientations and ledge density. Results show the precipitates widen and thicken by a ledge mechanism following parabolic growth laws. Morphology of precipitates during aging is closely related to the ledge density. Several types of defect emission from partially coherent interphase boundary in the alloy were observed using conventional and in situ hot stage TEM techniques. Prismatic dislocation loops expand and glide off from the precipitate. Perfect a/2 (110)_fcc dislocations glide away from the broad habit plane. Stacking faults emanated from the broad face of the laths were observed during precipitate growth. These defects result in steps in the interface and appear to compensate misfit in the broad face of the lath. / Ph. D.

This dissertation is concerned with the evaluation of a new statistically sound reconstruction methodology for continuous 3-D dynamic response fields of harmonically excited structures in steady-state vibration. This results in an experimental process which reconstructs the response field from a set of 3-D projections based on Laser-Doppler-Vibrometer (LDV) localized instantaneous velocity measurements. Included along with an estimate of the 3-D velocity field, are its statistical characteristics and the inferential tools required to test the quality of the estimation. This dissertation documents in detail the development and evaluation of the proposed reconstruction methodology and its relevant subprocesses which inc1ude the formulation of a deterministic laser-structure kinematic model, and regression models that afford statistical inference for the time-domain and spatial-domain structural dynamics, as well as for the projection recombination process. / Ph. D.

Turbine aerodynamic designers are currently focusing on unsteady passage flow to increase turbine performance. In particular, for high pressure turbine stages the effects of wakes and shocks shed from an upstream blade row on the downstream blade row need to be understood. Also, experimental data is needed for comparison with unsteady three-dimensional turbine stage calculations. Previous simulations of the unsteady shock/wake inlet flow field for a turbine rotor or stator used a rotating disk with radial bars upstream of a linear cascade. An alternate method of shock generation is developed here using a capped shock tube with multiple outlets to get a traveling system of three shock waves. Different lengths of tubing are used to get time delays between the shocks, which are then introduced at the top of a linear cascade of turbine blades and travel downwards (tangentially) along the leading edge. Advantages of this method include the absence of wakes and excellent two-dimensionality of the inlet shock waves. The period of the incoming shocks is easily adjustable to simulate different Strouhal numbers. Unsteady measurements of upstream total pressure, blade static pressures, and uncorrected downstream total pressure are made for a transonic mean flow with introduction of traveling shocks at M=1.3. An analytical solution (Bach and Lee, 1970) for the decay of cylindrical shock waves is used to estimate the behavior of flow variables other than pressure at the cascade inlet. The unsteady total pressure loss of the blade passage and the unsteady blade forces are measured with one shock passing and with three shocks passing at periods of 0.055 and 0.200 milliseconds. Loss is estimated as the normalized difference in unsteady total pressures and blade forces are integrated from seventeen unsteady surface pressure measurements. The Strouhal number for the 0.200 msec case is 2.9, which is typical of a high-pressure turbine nozzle or rotor. Periodic behavior in blade force and loss are observed for this case. Blade lift shows peak-to-peak variation of 6% and the estimated loss fluctuates by 100%. No change is observed in the average level of loss due to the incident shock waves. / Ph. D.

SiC whisker reinforced (Ca_0.6,Mg_0.4)Zr₄(PO₄)₆ (CMZP) matrix composites containing 10, 20, and 30 vol % whiskers were produced using a glass encapsulated hot isostatic pressing (HIPing) technique. The best HIPing temperature, pressure, and time conditions to optimize composite density and strength were determined to be 1050°C, 103 MPa, and 0.25 h. / Ph. D.

Policy case studies are presented on two congressional proposals that, if implemented, may result in implicit or explicit federal government endorsement of particular standards for the licensure or certification of teachers. They are, (a) authorization for the United States Department of Education to award design and implementation grants for programs of alternative teacher credentialing, and (b) appropriation of federal funds to support the National Board for Professional Teaching Standards. A discussion of the genesis of each proposal, a review of the legislative history of these two measures, and analysis of supporting rationale for each is included. Using an analytic framework based on the works of Deborah Stone and Thomas Green, it was determined that unresolved policy conflicts over teacher education governance and content led to federal attention to matters of teacher certification and licensure. / Ph. D.

Accurate and efficient numerical algorithms for solving the three dimensional Navier Stokes equations with a generalized thermodynamic and chemistry model and a one equation turbulence model on structured and unstructured mesh topologies are presented. In the thermo-chemical modeling, particular attention is paid to the modeling of the chemical source terms, modeling of equilibrium thermodynamics, and the modeling of the non-equilibrium vibrational energy source terms. In this work, nonequilibrium thermo-chemical models are applied in the unstructured environment for the first time. A three-dimensional, second-order accurate k-exact reconstruction algorithm for the inviscid and viscous fluxes is presented. Several new methods for determining the stencil required for the inviscid and viscous k-exact reconstruction are discussed. A new simplified method for the computation of the viscous fluxes is also presented. Implementation of the one equation Spalart and Allmaras turbulence model is discussed. In particular, an new integral formulation is developed for this model which allows flux splitting to be applied to the resulting convective flux. Solutions for several test cases are presented to verify the solution algorithms discussed. For the thermo-chemical modeling, inviscid solutions to the three dimensional Aeroassist Flight Experiment vehicle and viscous solutions for the axi-symmetric Ram-II C are presented and compared to experimental data and/or published results. For the hypersonic AFE and Ram-II C solutions, focus is placed on the effects of the chemistry model in flows where ionization and dissociation are dominant characteristics of the flow field. Laminar and turbulent solutions over a flat plate are presented and compared to exact solutions and experimental data. Three dimensional higher order solutions using the k-exact reconstruction technique are presented for an analytic forebody. / Ph. D.

A new approach to determining mode vectors is presented which uses predetermined global parameters and an improved residual model to iteratively determine modal residues. The motivation for such a technique is to determine modal parameters rapidly so that, as data acquisition techniques become faster, more structural degrees of freedom can be measured without significantly slowing down the parameter estimation process. The technique requires an accurate determination of the global parameters of natural frequency and damping by means of an FRF curve fit. More than one structural point is recommended to determine the global parameters since they will be used in determining the mode vectors. A structurally damped curve fitter which uses one or two FRFs is described and can be used for determining the global parameters. Examples of curve fitting simulated and measured data are presented and a comparison is made to a commercially available curve-fitter. Once a frequency range-of-interest is selected, frequencies will be chosen at which the mobility is measured using sine excitation. The in-range modal response is represented by a matrix-vector product where the vector contains the residues for the modes of interest. The out-of-range modal content is also represented by a matrix-vector product and forms the improved residual model. The residual content is removed from the measured mobility by an iterative technique which allows for an accurate determination of the residues of interest. An evaluation of the technique is carried out by simulating a dynamic system including the shaker and power supply. The simulated system is closely modeled after a real system used to evaluate the technique on experimental data. Convergence rates are shown for cases of close modes, low amplitude modes and errors in the global parameters. The results of using the technique on experimental data shows that convergence typically occurs in under 15 iterations. Regenerating the FRF from the modal parameters shows close agreement to the original FRF and better agreement than the regeneration from modal parameters derived from a commercially available curve fitter.> / Ph. D.