This thesis is divided into 8 sections: synthesis and characterization (char.) of Ba{sub 3}Mo{sub 18}O{sub 28} (an oligomer with four traps edge-sharing Mo octahedra); synthesis and char. of K{sub x}M{sub y}Mo{sub 14}O{sub 22} (M=Sn, Pb, Sr) (oligomers with three traps edge-sharing Mo octahedra); synthesis and char. of K{sub 0.19}Ba{sub 3.81}Mo{sub 22}O{sub 34} (an oligomer with five traps edge-sharing Mo octahedra); synthesis and char. of Ti{sub 0.31}Fe{sub 1.69}Mo{sub 4}O{sub 7} (a material containing closest-packing of infinite chains of octahedral Mo clusters); synthesis and char. of K{sub x}M{sub 2-x}Mo{sub 10}O{sub 16} (M=Ca, Sr, Gd) (oligomers with two traps edge-sharing Mo octahedra); synthesis and char. of the RE{sub 4}Mo{sub 4}O{sub 11} series; synthesis and char. of Pb{sub 0. 31}WO{sub 3} (a tetragonal tungsten bronze containing lead); and examination of superstructure in Fe{sub 1.89}Mo{sub 4.11}O{sub 7}, Sn{sub 0.9}Mo{sub 4}O{sub 6}, InMo{sub 4}O{sub 6}, and Mn{sub 1. 5}Mo{sub 8}O{sub 11} by electron microscopy.

Polystyrene divinylbenzene was modified by acetyl, sulfonic acid, and quaternary ammonium groups. A resin functionalized with an acetyl group was impregnated in a PTFE membrane and used to extract and concentrate phenolic compounds from aqueous samples. The acetyl group created a surface easily wetted, making it an efficient adsorbent for polar compounds in water. The membrane stabilized the resin bed. Partially sulfonated high surface area resins are used to extract and group separate an aqueous mixture of neutral and basic organics; the bases are adsorbed electrostatically to the sulfonic acid groups, while the neutraons are adsorbed hydrophobically. A two-step elution is then used to separate the two fractions. A partially functionalized anion exchange resin is used to separate organic acids and phenols from neutrals in a similar way. Carboxylic acids are analyzed by HPLC and phenols by GC.

The purpose of the Human Genome Project is outlined followed by a discussion of electrophoresis in slab gels and capillaries and its application to deoxyribonucleic acid (DNA). Techniques used to modify electroosmotic flow in capillaries are addressed. Several separation and detection schemes for DNA via gel and capillary electrophoresis are described. Emphasis is placed on the elucidation of DNA fragment size in real time and shortening separation times to approximate real time monitoring. The migration of DNA fragment bands through a slab gel can be monitored by UV absorption at 254 nm and imaged by a charge coupled device (CCD) camera. Background correction and immediate viewing of band positions to interactively change the field program in pulsed-field gel electrophoresis are possible throughout the separation. The use of absorption removes the need for staining or radioisotope labeling thereby simplifying sample preparation and reducing hazardous waste generation. This leaves the DNA in its native state and further analysis can be performed without de-staining. The optimization of several parameters considerably reduces total analysis time. DNA from 2 kb to 850 kb can be separated in 3 hours on a 7 cm gel with interactive control of the pulse time, which is 10 times …

The polarization of {tau} leptons produced in the reaction e{sup +}e{sup {minus}} {yields} {tau}{sup +}{tau}{sup {minus}} near the peak of the Z{degree} resonance has been measured using a sample of 24904 {tau}{sup +}{tau}{sup {minus}} events, with an estimated background of 1.5%. We have selected 4562 {tau} {yields} e{nu}{bar {nu}} 2218 {tau} {yields} {pi}{nu} and 5133 {tau} {yields} {rho}{nu} candidates. The mean value obtained is P{sub {tau}} = {minus}0.176 {plus_minus} 0.029. This corresponds to a ratio of the neutral current vector to the axial-vector coupling constants of the {tau} lepton of g{sub V}{sup {tau}}/g{sub A}{sup {tau}} = 0.088 {plus_minus} 0.014. This leads to a value of the electroweak mixing angle of sin{sup 2}{theta}{sub W} = 0.2280 {plus_minus} 0.0036. This result is in good agreement with previous measurements of the weak mixing angle from the study of the Z{degree} lineshape and the forward-backward asymmetries in the processes Z{degree} {yields} l{sup +}l{sup {minus}} and Z{degree} {yields} q{bar q}.

Addition of nonmetal interstitial atoms to Zr-Ni compounds has resulted in several new phases. A single-crystal x-ray study was carried out for Zr{sub 3}NiO. Zr{sub 4}Ni{sub 2}O is a high- temperature phase, forming in samples annealed at 1250 C. Huekel band calculations led to prediction and confirmation of additional phases in more electron rich systems. Other phases studied by XRD are Zr{sub 6}Ni{sub 4}Ti{sub 2}O{sub 0.6}, Nb{sub 6}Ni{sub 6}O, and Nb{sub 6}Ni{sub 4}Ta{sub 2}O{sub 2}. Phases identified by powder diffraction are Nb{sub 4}Ni{sub 2}O, Zr{sub 4}Cu{sub 2}O, and Zr{sub 6}Co{sub 4}Ti{sub 2}O. New Zr kappa phases in space group P6s{sub 3}/mmc were found: Zr{sub 9}Mo{sub 4}SO{sub x} and Zr{sub 9}W{sub 4}(S,Ni)O{sub 3}. A new structure type was discovered with Zr{sub 6}Ni{sub 6}TiSiO{sub 1.8}. In all these interstitially stabilized phases, O is coordinated in Zr octahedral; there are no Ni-O interactions.

This dissertation contains investigations in three distinct areas. Chapters 1 and 2 provide an analysis of the effects of electromagnetic phenomena during the initial stages of cell discharge. Chapter 1 includes the solution to Maxwell`s equations for the penetration of the axial component of an electric field into an infinitely long cylindrical conductor. Chapter 2 contains the analysis of the conductor included in a radial circuit. Chapter 3 provides a complete description of the equations that describe the growth of an oxide film. A finite difference program was written to solve the equations. The system investigated is the iron/iron oxide in a basic, aqueous solution. Chapters 4 and 5 include the experimental attempts for replacing formaldehyde with an innocuous reducing agent for electroless deposition. In chapter 4, current-versus-voltage curves are provided for a sodium thiosulfate bath in the presence of a copper disk electrode. Also provided are the cathodic polarization curves of a copper/EDTA bath in the presence of a copper electrode. Chapter 5 contains the experimental results of work done with sodium hypophosphite as a reducing agent. Mixed-potential-versus-time curves for solutions containing various combinations of copper sulfate, nickel chloride, and hypophosphite in the presence of a palladium disk electrode …

A thermal building simulation program is a numerical model that calculates the response of the building envelopes to weather and human activity, simulates dynamic heating and cooling loads, and heating and cooling distribution systems, and models building equipment operation. The scope of the research is to supply the users of such programs with information about the dangers and benefits of simplifying the input to their models. The Introduction describes the advantages of modeling the heat transfer mechanisms in a building. The programs that perform this type of modeling have, however, limitations. The user is therefore often put in the situation of simplifying the floor plans of the building under study, but not being able to check the effects that this approximation introduces in the results of the simulation. Chapter 1 is a description of methods. It also introduces the floor plans for the office building under study and the ``reasonable`` floor plans simplifications. Chapter 2 presents DOE-2, the thermal building simulation program used in the sensitivity study. The evaluation of the accuracy of the DOE-2 program itself is also presented. Chapter 3 contains the sensitivity study. The complicated nature of the process of interpreting the temperature profile inside a space …

This thesis is divided into 4 parts: a review, ion chromatography of metal cations on carboxylic resins, separation of hydrophilic organic acids and small polar compounds on macroporous resin columns, and use of eluent modifiers for liquid chromatographic separation of carboxylic acids using conductivity detection.

Nuclear Magnetic Resonance (NMR) and Nuclear Quadrupole Resonance (NQR) techniques have been very successful in obtaining molecular conformation and dynamics information. Unfortunately, standard NMR and NQR spectrometers are unable to adequately detect resonances below a few megahertz due to the frequency dependent sensitivity of their Faraday coil detectors. For this reason a new spectrometer with a dc SQUID (Superconducting Quantum Interference Device) detector, which has no such frequency dependence, has been developed. Previously, this spectrometer was used to observe {sup 11}B and {sup 27}Al NQR resonances. The scope of this study was increased to include {sup 23}Na, {sup 51}V, and {sup 55}Mn NQR transitions. Also, a technique was presented to observe {sup 14}N NQR resonances through cross relaxation of the nitrogen polarization to adjacent proton spins. When the proton Zeeman splitting matches one nitrogen quadrupoler transition the remaining two {sup 14}N transitions can be detected by sweeping a saturating rf field through resonance. Additionally, simultaneous excitation of two nitrogen resonances provides signal enhancement which helps to connect transitions from the same site. In this way, nitrogen-14 resonances were observed in several amino acids and polypeptides. This spectrometer has also been useful in the direct detection of methyl quantum tunneling splittings …

This thesis studies memory bandwidth as a performance predictor of programs. The focus of this work is on computationally intensive programs. These programs are the most likely to access large amounts of data, stressing the memory system. Computationally intensive programs are also likely to use highly optimizing compilers to produce the fastest executables possible. Methods to reduce the amount of data traffic by increasing the average number of references to each item while it resides in the cache are explored. Increasing the average number of references to each cache item reduces the number of memory requests. Chapter 2 describes the DLX architecture. This is the architecture on which all the experiments were performed. Chapter 3 studies memory moves as a performance predictor for a group of application programs. Chapter 4 introduces a model to study the performance of programs in the presence of memory hierarchies. Chapter 5 explores some compiler optimizations that can help increase the references to each item while it resides in the cache.

Matrix-assisted laser desorption (MALD) is a technique for converting large biomolecules into gas phase ions. Some characteristics of the commonly used uv matrices are determined. Solubilities in methanol range from 0.1 to 0.5 M. Solid phase absorption spectra are found to be similar to solution, but slightly red-shifted. Acoustic and quartz crystal microbalance signals are investigated as possible means of uv-MALD quantitation. Evidence for the existence of desorption thresholds is presented. Threshold values are determined to be in the range of 2 to 3 MW/cm{sup 2}. A transient imaging technique based on laser-excited fluorescence for monitoring MALD plumes is described. Sensitivity is well within the levels required for studying matrix-assisted laser desorption, where analyte concentrations are significantly lower than those in conventional laser desorption. Results showing the effect of film morphology, particularly film thickness, on plume dynamics are presented. In particular, MALD plumes from thicker films tend to exhibit higher axial velocities. Fluorescent labeling of protein and of DNA is used to allow imaging of their uv-MALD generated plumes. Integrated concentrations are available with respect to time, making it possible to assess the rate of fragmentation. The spatial and temporal distributions are important for the design of secondary ionization schemes …

A chemical synthesis route is discussed which results in a low- temperature precursor to Y-Ba-Cu-O ceramics; it is based on use of molten Ba(OH){sub 2}{center_dot}8H{sub 2}O flux. Two different chemical systems have been examined; the first one, based on nitrate salts, has been demonstrated to be a viable precursor material for tape casting and extrusion; the second, made from acetate salts, has been used for powder synthesis and extrusion. Rheology of pastes shows that their flow may be fit to either Bingham Plastic or Hershel- Bulkley models. Yield stress is controlled in both pastes by volume fraction solids. Viscosity also follows solids loading in the paste. Shear thinning is controlled by colloidal nature of precursor. The paste has colloidal microstructure. Comparison of concentric cylinder rheometry and piston extrusion rheometry shows order of magnitude differences in yield stress, resulting from the test method and paste dilation.

In this dissertation, the step-by-step development of a scalable parallel hierarchical radiosity renderer is documented. First, a new look is taken at the traditional radiosity equation, and a new form is presented in which the matrix of linear system coefficients is transformed into a symmetric matrix, thereby simplifying the problem and enabling a new solution technique to be applied. Next, the state-of-the-art hierarchical radiosity methods are examined for their suitability to parallel implementation, and scalability. Significant enhancements are also discovered which both improve their theoretical foundations and improve the images they generate. The resultant hierarchical radiosity algorithm is then examined for sources of parallelism, and for an architectural mapping. Several architectural mappings are discussed. A few key algorithmic changes are suggested during the process of making the algorithm parallel. Next, the performance, efficiency, and scalability of the algorithm are analyzed. The dissertation closes with a discussion of several ideas which have the potential to further enhance the hierarchical radiosity method, or provide an entirely new forum for the application of hierarchical methods.

Goal is to study the organization and structures of guest atoms and molecules and their reactions on internal surfaces within pores of zeolites and aluminophosphate molecular sieves. {sup 27}Al and {sup 23}Na double rotation NMR (DOR) is used since it removes the anisotropic broadening in NMR spectra of quadrupolar nuclei, thus increasing resolution. This work concentrates on probing aluminum framework atoms in aluminophosphate molecular sieves and sodium extra framework cations in porous aluminosilicates. In aluminophosphates, ordering and electronic environments of the framework {sup 27}Al nuclei are modified upon adsorption of water molecules within the channels; a relation is sought between the sieve channel topology and the organization of adsorbed water, as well as the interaction between the Al nuclei and the water molecules. Extra framework Na{sup +} cations are directly involved in adsorption processes and reactions in zeolite cavities.

This thesis is divided into 3 papers: dynamical low-energy electron- diffraction investigation of lateral displacements in topmost layer of Pd(110); determination of (1{times}1) and (1{times}2) structures of Pt thin films on Pd(110) by dynamical low-energy electron-diffraction analysis; and structural determination of a NiO(111) film on Ni(100) by dynamical low-energy electron-diffraction analysis.

After a general introduction, this thesis is divided into 3 parts: indirect fluorescence detection of sugars separated by capillary zone electrophoresis with visible laser excitation, absorption detection in capillary electrophoresis by fluorescence energy transfer, and increased selectivity for electrochromatography by dynamic ion exchange.

This report neutron radiography measuring methods and the neutron radiography model.

Hale and Cohen (1991) developed software to generate two-dimensional computer models of complex geology. Their method uses a triangulation technique designed to support efficient and accurate computation of seismic wavefields for models of the earth`s interior. Subsequently, Hale (1991) used this triangulation approach to perform dynamic ray tracing and create synthetic seismograms based on the method of Gaussian beams. Here, I extend this methodology to allow an increased variety of ray-theoretical experiments. Specifically, the developed program GBmod (Gaussian Beam MODeling) can produce arbitrary multiple sequences and incorporate attenuation and density variations. In addition, I have added an option to perform Fresnel-volume ray tracing (Cerveny and Soares, 1992). Corrections for reflection and transmission losses at interfaces, and for two-and-one-half-dimensional (2.5-D) spreading are included. However, despite these enhancements, difficulties remain in attempts to compute accurate synthetic seismograms if strong lateral velocity inhomogeneities are present. Here, these problems are discussed and, to a certain extent, reduced. I provide example computations of high-frequency seismograms based on the method of Gaussian beams to exhibit the advantages and disadvantages of the proposed modeling method and illustrate new features for both surface and vertical seismic profiling (VSP) acquisition geometries.

Water-enhanced solvation (WES) was explored for Lewis acid solutes in Lewis base organic solvents, to develop cheap extract regeneration processes. WES for solid solutes was determined from ratios of solubilities of solutes in water-sat. and low-water solvent; both were determined from solid-liquid equilibrium. Vapor-headspace analysis was used to determine solute activity coefficients as function of organic phase water concentration. WES magnitudes of volatile solutes were normalized, set equal to slope of log {gamma}{sub s} vs x{sub w}/x{sub s} curve. From graph shape {Delta}(log {gamma}{sub s}) represents relative change in solute activity coefficient. Solutes investigated by vapor-headspace analysis were acetic acid, propionic acid, ethanol, 1,2-propylene glycol, 2,3-butylene glycol. Monocarboxylic acids had largest decrease in activity coefficient with water addition followed by glycols and alcohols. Propionic acid in cyclohexanone showed greatest water-enhancement {Delta} (log {gamma}{sub acid})/{Delta}(x{sub w}/x{sub acid}) = {minus}0.25. In methylcyclohexanone, the decrease of the activity coefficient of propionic acid was {minus}0.19. Activity coefficient of propionic acid in methylcyclohexanone stopped decreasing once the water reached a 2:1 water to acid mole ratio, implying a stoichiometric relation between water, ketone, and acid. Except for 2,3-butanediol, activity coefficients of the solutes studied decreased monotonically with water content. Activity coefficient curves of ethanol, 1,2-propanediol …

The low temperature and flux dependent growth of ultrathin Ag films on the Si(111)7x7 surface is studied with Reflection High-Energy Electron Diffraction (RHEED). The grazing incidence geometry of RHEED allows for an incident molecular beam normal to the surface, and makes it an ideal surface probe for studying ultrathin film growth in real time. Short-lived oscillations in the diffracted intensity are observed during Ag deposition at 150 K, indicating quasi-layer-by-layer growth mediated by adatom mobility. When the 150 K growth is performed over a wide range of deposition rates F, the peak intensity is observed to scale, i.e. I(Ft) depends only on the total amount deposited, which implies thermally activated diffusion is absent at 150 K. Scaling is not obeyed at higher temperatures (T{ge}473 K) for the growth of the {radical}3{times}{radical}3 R30{degrees} ({radical}3) superstructure. Testing for scaling of the diffracted intensity constitutes a new experimental method which can be applied generally to determine if thermal diffusion is active at a particular temperature. Scaling is consistent with a constant diffusion length R{sub 0}, independent of substrate temperature and deposition rate. The presence of a non-thermal diffusion mechanism (responsible for the constant diffusion length R{sub 0}) is confirmed by monitoring the flux …