Chemistry Commons^™

Characterizing And Monitoring Changes In State Of Polymers During Cure And Use -Aging, Andrew Orschel Meyer

Dissertations, Theses, and Masters Projects

Multi Angle Laser Light Scattering (MALLS) and Frequency Dependent Electromagnetic Sensing (FDEMS) provide unique characterizations of polymer systems during cure and use-aging. This research illustrates how MALLS is an extremely accurate technique for absolute characterization of macromolecules, giving molecular weight and size information that other widely used and accepted techniques are incapable of measuring. Application of MALLS to monitoring the changing state of a polyamide-11 system in a water aging environment led to the discovery of an equilibrium molecular weight which is the result of two competing reactions, hydrolysis-degradation and a newly discovered recombination-polymerization reaction. The discovery of this recombination …

Solid State Nmr Characterization Of Structural And Motional Parameter Distributions In Polyamidoammonium Dendrimers, Dariya Ivanovna Malyarenko

Dissertations, Theses, and Masters Projects

The characterization of narrow distributions of structural and motional parameters, and their evolution during the broad glass transition, is performed for deuterated PAMAM dendrimer salts using solid state NMR. The broadening of deuteron quadrupole echo (QE) lineshapes is consistent with the presence of narrow hydrogen bond length distribution (sigmar < 0.25 A) at the spacer amide and branching tertiary amine sites. The temperature dependent averaging of the experimental lineshapes is explained on the basis of fast planar librations in the dendrimer interior, and fast rotation and intermediate regime libration (in an asymmetric cone) of the dendrimer termini. The amplitudes of libration are temperature dependent and higher for low generation dendrimers, while librational rates show Arrhenius behavior only within the glass transition region. In this region, the width of log-normal distribution of rates increases with temperature at sites associated with chlorine counterions. The largest distributions are still less than one order of magnitude wide, unlike the dendrimer in solution or the linear polymers. Interpenetrated low generations (G < 3), uniform intermediate generations (G = 3--5) with surface network, and backfolded high generations (G > 5), are distinguished by interior and termini dynamics.;In the regime of fast motion QE lineshapes are highly sensitive to the presence of narrow structural and motional parameter distributions, and provide constraints on motional geometry independent of rates. The precise characterization of narrow log-normal rate distributions in the intermediate regime can be …

Hybrid Quantum And Molecular Mechanics Embedded Cluster Models For Chemistry On Silicon And Silicon Carbide Surfaces, James R. Shoemaker

Theses and Dissertations

Fabrication of silicon carbide SiC semiconductor devices are of interest for aerospace applications because of their high-temperature tolerance. Growth of an insulating SiO₂ layer on SiC is a poorly understood process, and sometimes produces interface defects that degrade device performance. Accurate theoretical models of surface chemistry, using quantum mechanics QM, do not exist because of the huge computational cost of solving Schroedingers equation for a molecular cluster large enough to represent a surface. Molecular mechanics MM, which describes a molecule as a collection of atoms interacting through classical potentials, is a fast computational method, good at predicting molecular structure, …

Computer Modeling Of Molecular Vibration Frequencies And Its Application To The Modeling Of Silane Compounds, Ryan T. Merrell

Honors Capstone Projects and Theses

No abstract provided.

Microstructural Characterization Of An Ultra-High-Performance Polyimide, April Heather Baugher

Dissertations, Theses, and Masters Projects

The motivation for this study was to further characterize a relatively new high-temperature polymer for application as a matrix resin for carbon fiber composites. The two primary questions addressed in this study dealt with the structural and chemical changes occurring in these polymers on exposure to high temperature.;To investigate the structural changes in the heat-treated samples, a positron annihilation lifetime spectrometer was designed, built and optimized. Because the lifetime of a positron in a material reflects the electronic structure of the material in which it annihilates, measurements by positron annihilation lifetime spectroscopy can be used to investigate changes in a …

Characterization Of Iron Oxides And Atmospheric Corrosion Of Steel, Sei Jin Oh

Physics Theses & Dissertations

The study of corrosion behavior was performed using three different analytical techniques, which provided information on the formation, development and layering of iron oxides on the corrosion products as a function of atmospheric conditions, exposure time and type of steel. In particular, the protective layer formed on weathering steel was investigated as a function of different amounts of alloying elements in the steel, atmospheric conditions and exposure times. Combined together, the results provided a better understanding of the atmospheric corrosion behavior of steel, and formed a part of database of the atmospheric corrosion characteristics.

Accurate characterization of the iron oxides …

Synthesis And Characterization Of Boron-Containing Polymeric Materials For Neutron Shielding Applications, Michael B. Glasgow

Dissertations, Theses, and Masters Projects

The development of boron-containing polymeric materials for neutron shielding applications was undertaken. Three types of materials were characterized for physical and thermal properties: boron powder-filled epoxy composites, carborane polyamides having boron chemically bonded into the polymer, and boron-loaded polyimide thin films. Addition of amorphous submicron boron powder did not affect significantly the thermal performance of the epoxy. The 17% boron loading produced a 26% increase in compressive failure strength and a 68% increase in the compressive modulus. 0.125 inch thick specimens containing 17% boron absorbed 92% of incident neutrons from a 5-Curie Pu/Be source compared with {dollar}<{dollar}1% for the neat epoxy. Dispersion of the boron in the epoxy was improved with the addition of larger size crystalline boron powders. Carborane polyamides containing up to 35% boron were thermally stable up to 400{dollar}\sp\circ{dollar}C in air. The polymers had hydrogen/boron ratios from 2.0 to 3.8 and were soluble in several organic solvents. Polymer solutions were processed into clear, colored thin films. Boron-filled polyamic acid solutions of a PMDA-ODA polyimide containing up to 10% boron were processed into thin films. Neutron absorption of the opaque films measured in a 5-Curie Pu/Be neutron source was linear with boron concentration and film thickness. The fraction of neutrons absorbed varied linearly with boron concentration and film thickness. The applicability of boron-containing materials to the aerospace, nuclear power and accelerator industries was investigated.

Study Of The Long-Term Desorption Of Trichloroethylene From Clay Soils Using Infrared Spectroscopy, Mary P. Stager

Theses and Dissertations

Slow desorption of contaminants from soil presents one of the greatest challenges to modeling contaminant fate and transport and implementing effective remediation technologies. The kinetics of long-term desorption of trichloroethylene (TCE) from powdered clay soils were studied to determine the desorption rates and mechanism. Infrared absorption spectroscopy was used to monitor the concentration of TCE desorbed from contaminated flint clay for 71 hours. Observed gas phase TCE concentrations as a function of time were compared to that predicted by a one-site Langmuir desorption mechanism. The Langmuir model, with a single type of bonding site, did not account for the release …

Calculations Of The Interactions Of Energetic Ions With Materials For Protection Of Computer Memory And Biological Systems, Myung-Hee Y. Kim

Dissertations, Theses, and Masters Projects

Theoretical calculations were performed for the propagation and interactions of particles having high atomic numbers and energy through diverse shield materials including polymeric materials and epoxy-bound lunar regolith by using transport codes for laboratory ion beams and the cosmic ray spectrum. Heavy ions fragment and lose energy upon interactions with shielding materials of specified elemental composition, density, and thickness. A fragmenting heavy iron ion produces hundreds of isotopes during nuclear reactions, which are treated in the solution of the transport problem used here. A reduced set of 80 isotopes is sufficient to represent the charge distribution, but a minimum of …

First Principles Linear Response Calculations Of Lattice Dynamics, Cheng-Zhang Wang

Dissertations, Theses, and Masters Projects

First principles calculations, using the density-functional theory and particularly the local density approximation (LDA), have achieved remarkable success in studying the properties of solid state systems. Although the basic results of these calculations are the electronic structures (eigenvalues, eigenfunctions, etc.) and the total energy of ground state, many other related physical properties can be deduced from them by investigating their response under external perturbations. Using the linear response method with linearized-augmented-plane-wave (LAPW) basis, we have calculated lattice dynamical properties of important semiconductors CuCl, SiC and ferroelectric KNbO{dollar}\sb3.{dollar} CuCl is known to exhibit large anharmonic effects and possibly a complicated multi-well …

A Study Of Molecular Order And Motion In Nematic Liquid Crystal Mixtures, Jon Michael Goetz

Dissertations, Theses, and Masters Projects

Materials which flow like fluids, but possess anisotropic properties like molecular crystals, are called 'liquid crystals'. Studies of liquid crystals contribute to our understanding of how molecular orientation influences macroscopic properties. This thesis presents experimental and theoretical investigations of molecular order and dynamics in nematic liquid crystal systems. First, deuterium nuclear magnetic resonance is used to determine the degree of orientational order of both components of a liquid crystal mixture simultaneously. The temperature dependence of the four order parameters is interpreted using a newly developed mean field theory of nematic binary mixtures composed of biaxial molecules. Next, mean field theory …

Investigation Of Alignment Dynamics In Mg-Ne And Mg-Ar Two-Photon Fractional Collisions, David Allen Olsgaard

Physics Theses & Dissertations

A new technique is used to observe the dynamics of electronic alignment in a dissociating collision complex. The technique requires the absorption of two optical photons during a single binary collision. Two exciting light fields are tuned into the wings of the 3s¹s₀-3p₁ and 3p¹p₁-5s¹s₀ resonances of Mg where strong collisions with rare gas atoms induce transitions between corresponding molecular states. The alignment produced in the intermediate state by the first excitation is probed by the second laser as a function of relative linear laser polarization and laser …

Single And Double Ionization Of Helium By Highly Charged Sulfur Ions, Karen M. Lifrieri

Masters Theses

Single and double ionization of helium by highly charged sulfur projectiles is investigated over an energy range of 0.16 to 1.6 MeV/u. Absolute cross sections for the processes of pure ionization, ionization associated with single capture, and ionization associated with single loss by S^6,13+ projectiles were experimentally determined and compared with previous results and theories. Ratios of double-tosingle ionization for each outgoing projectile charge state were also determined and compared with theory. The pure ionization ratios for S⁶⁺ at the highest energies investigated show the q²/E dependence predicted by Knudsen et al. (1984). For S^{13+ …}

Studies Of Radiation Effects In Three High Polymers, Heidi Rene-Mitchell Ries

Physics Theses & Dissertations

Three high polymers, Mylar®, Ultem®, and Kapton®, were irradiated to total doses of 1, 5, and 9.5 gigarad using 1-MeV electrons. The glass transition temperatures (T_g) of the materials before and after irradiation were measured using an AC electrical dissipation factor technique. From the T_g data, it was found that the electron radiation at these total doses results in net chain scissioning in Mylar and net crosslinking in Ultem, while self-mending is predominant in Kapton. The dielectric constant was measured before and after irradiation, but no significant changes due to irradiation were observed. Electron paramagnetic resonance (EPR) …

The Design And Construction Of Microprocessor-Computer Controlled Rapid Scanning Fiberoptic Spectrophotometer, Kathleen Marie Tobin

Masters Theses

Conventional spectrophometers require the transfer of a sample to a cuvette for obtaining spectra. The measurement of absorbance in situ can be accomplished using a fiber optic probe which can be placed directly in the sample. The fiber optic probe also minimizes environmental factors such as thermal or vibrational which may affect the absorbing species. A rapid scanning speed allows for essentially simultaneous wavelength monitoring.

The effect of coupling a rapid scanning spectrophotometer with a fiber optic probe provides for an extremely versatile system. When used in comjunction with a microprocessor or computer, this approach offers advantages such as data …

A Laser Interferometric Study Of Electric Field Effects On Methane-Oxygen Flame Plasmas, Mark D. Prairie

Masters Theses

A laser interferometer is developed to study the refractive index field, aerodynamic structure, and three dimensional temperature profile of a methane-oxygen flame system under the influence of D.C. electric fields. A combined graphical-numerical method is used to transform the observed interference patterns into radial temperature distributions. The results indicate that the electric field exerts a marked influence on the flame stability, geometry, and charged particle flow. Experimental evidence shows that these effects are most apparent under fuel rich conditions. It is suggested an electric field may change the concentration gradients of reacting species, leading to an altered course of fuel …

Evidence For The Existence Of Two Stable Sites For Cobalt Impurity Atoms In Aluminum, Arun Venkatachar

Dissertations and Theses

Using Fe⁵⁷Mössbauer spectroscopy, two alternative sites occupied by cobalt (10^-4 at. % ) impurity atoms in aluminum have been isolated. The substitutional site A is the stable position after annealing the sample above 840 K, followed by a rapid quench. The impurity atoms in site A are characterized by a single line Mössbauer spectrum (indicative of a cubic environment), a room-temperature f = 0.502 (r. m. s. displ. 0.071 A) and an I. S. (reI. to Fe) = -0.421 mm/sec. For anneals below 770 K the cobalt atoms migrate to site B, which is characterized by a …

On The Physical Properties Associated With Omega Phase In Titanium-Chromium Alloys, Serag El Din El Sayed Habib

Archived Theses and Dissertations

No abstract provided.

Investigation Of The Alpha-Sub-Gamma Phase In Alnico 6, Cortez Samuel

Dissertations and Theses

The purpose of this research project was to study the αᵧ phase in Alnico 6. Other phases were studies for comparison. Also the effect of an applied magnetic field on the formation of the αᵧ phase was investigated.

Three single crystals of Alnico 6 were heat treated for one hour—one at 1250°C, one at 1000°C, and one at 800°C—and water-quenched. The microstructure of each sample was observed with the optical microscope, and X-ray diffraction patterns were taken to determine the crystal structure of the phases present.

Several single crystal samples of Alnico 6 were heat treated at 1000°C and furnace-cooled. …

Properties And Structure Of Some Chalcogenide Glasses, Amin Ismail Amin Abdel-Latif

Archived Theses and Dissertations

No abstract provided.

Catalytic Decomposition Of Hydrogen Peroxide By Manganese-Doped Magnesium Hydroxide, Nabih Philobbos Kelada

Archived Theses and Dissertations

No abstract provided.

The Electrical Resistivity Of Different Types Of Glasses, Fadel Youssef Iskandar Assabghy

Archived Theses and Dissertations

No abstract provided.

Investigation Of The Platinum-Rich Portion Of The Platinum-Tantalum Phase Diagram, Bob Dean Browning

Theses and Dissertations

The Pt-Ta binary system was investigated at two isotherms;1000°C and 1500°C, and at eleven alloy compositions in the range of 50 to 100 atomic percent platinum. The alloys were examined by x-ray diffraction and metallography. Three intermetallic compounds, Pt₂Ta, Pt₃Ta, and Pt₄Ta were found to exist in this composition range. The Pt₄Ta intermetallic appeared only at the 1500°C isotherm. Platinum dissolved tantalum substitutionally to 90 atomic percent at 1500 °C and to approximately 80 atomic percent at 1000 °C.

Scholasticism An Intellectual Basis And Unifying Principle Of Modern Science, Alice V. Johnson

Electronic Thesis and Dissertation

Amid the almost uninterrupted disintegration of systems during the last three centuries, the philosophy of St. Thomas has alone been able to stand the shock of criticism; it alone has proved sufficiently solid and comprehensive to serve as an intellectual basis and unifying principle for all the new facts and phenomena brought to light by modern science.