Physical Sciences and Mathematics Commons^™

Stoichiometric Determination Of Hydride Materials At Extreme Conditions, Gregory Alexander Smith

UNLV Theses, Dissertations, Professional Papers, and Capstones

Hydrogen was predicted to be a high-temperature superconductor at near-megabar conditions in 1968,[1] but only recently was been experimentally observed.[2] This is due to the extraneous metrological constraint of requiring 5 megabars of pressure to stabilize. A more practical approach for synthesis of high-temperature superconductors has been pro-posed through the use of hydride compounds. Recently, a surge of rare earth hydrides have achieved critical superconducting transition temperatures (T_C ) close to room temperature.[3, 4, 5, 6] However, due to limitations of the necessary instrumentation to achieve megabar pressures, many techniques traditionally used to measure stoichiometry are unavailable.Three works presented in …

Developments Of Machine Learning Potentials For Atomistic Simulations, Howard Yanxon

UNLV Theses, Dissertations, Professional Papers, and Capstones

Atomistic modeling methods such as molecular dynamics play important roles in investigating time-dependent physical and chemical processes at the microscopic level. In the simulations, energy and forces, sometimes including stress tensor, need to be recalculated iteratively as the atomic configuration evolves. Consequently, atomistic simulations crucially depend on the accuracy of the underlying potential energy surface. Modern quantum mechanical modeling based on density functional theory can consistently generate an accurate description of the potential energy surface. In most cases, molecular dynamics simulations based on density functional theory suffer from highly demanding computational costs. On the other hand, atomistic simulations based on …

Investigations Of Technetium Metal And The Synthesis Of Binary Technetium Nitrides Under Extreme Conditions, Emily Siska

UNLV Theses, Dissertations, Professional Papers, and Capstones

Technetium (Tc) is the lightest of the radioactive elements and has no stable isotopes. Significant quantities of Tc are not naturally occurring on earth. However, technetium is found in high fission yield in nuclear reactors and produced for medical imaging. With its long half life, and high mobility in the environment make it of particular interest. To that end, the fundamental chemistry of Tc and Tc compounds is not as well understood compared to neighboring elements on the periodic table. Therefore, fundamental studies designed to better understand this transition metal, coupled with more targeted investigation at high temperature and pressure …

Chemical And Electronic Surface Structure Of Chalcopyrite-Based Thin Films For Solar Water Splitting, James C. Carter

UNLV Theses, Dissertations, Professional Papers, and Capstones

In recent years, various thin film solar devices have reached markedly high efficiencies on both the laboratory and large area scale. To further evaluate their potential, and help drive device optimization of efficient solar devices, a detailed understanding of the chemical and electronic structure of the surfaces and interfaces is required. It is these interfaces that play a pivotal role in dictating aspects of device performance. Chalcopyrite-based materials, such as Cu(In,Ga)S2 (CIGS) are regarded as one of the most promising absorber materials for use in highly efficient solar devices. In the context of photoelectrochemical (PEC) hydrogen generation, the tunability of …

Optimization Of Useful Hard X-Ray Photochemistry, David Lewis Goldberger

UNLV Theses, Dissertations, Professional Papers, and Capstones

X-ray induced damage is generally considered a nuisance, but in the field of Useful Hard X-ray Photochemistry we harness the highly ionizing and penetrating properties of hard X-rays (> 7 keV) to initiate novel photochemical decomposition and synthesis at ambient and extreme conditions. Preliminary experiments suggest that the energy of irradiating photons and the sample pressure play roles in determining the nature of X-ray induced damage. Here, we present the X-ray energy dependence of damage induced in strontium oxalate, strontium nitrate, and barium nitrate, as well as the pressure dependence of X-ray induced damage of strontium oxalate. Our results indicate …

The Electrochemical Deposition Of Samarium And Europium Dissolved In Ionic Liquid Solvent, Bea Martinez

UNLV Theses, Dissertations, Professional Papers, and Capstones

Rare-earth elements include the lanthanide series in the periodic table with the addition of scandium and yttrium. China produces approximately 95% of the world’s rare-earths supply and is the largest consumer of the world’s rare earth supply. Domestic production of rare-earth metals is a priority in the US. The domestic demand for rare-earth elements is largely based on their use in electronic devices, catalytic converters, and more importantly defense applications. Therefore, China’s monopoly of rare-earth elements is viewed as a threat to national security. Although capital investments have resulted in an increase in domestic mining and refining of rare-earth materials, …

Surface And Interface Characterization Of Solution-Processed Metal Oxides And Pedot:Pss Using Photoelectron Spectroscopy, Lynette M. Kogler

UNLV Theses, Dissertations, Professional Papers, and Capstones

Solution-processed materials are appealing for use in printable electronics as a means to lower production costs, but precise control of the process is crucial for achieving the desired properties in the final materials and their interfaces. Electronic interface properties depend on both the involved materials and their fabrication processes, impacting the development and commercialization of these materials. Analyzing the chemical and electronic structure of these materials, particularly at the surfaces and interfaces, is important not only for insuring that the materials have the desired properties, but also for understanding the effects of the fabrication process and how to modify properties …

Structural Behavior Of Nbsexte2-X Superconductors Under High Pressure, Vahe Mkrtchyan

UNLV Theses, Dissertations, Professional Papers, and Capstones

Niobium chalcogenide compounds have recently gained a great deal of interest due to the fact that a superconducting phase coexists with the charge density wave state (CDW), as well as their potential for numerous applications. Two superconducting compositions, NbSexTe2-x (x=2, 1.5) were prepared by solid state route using high purity Nb, Se, and Te powders. Powder X-ray diffraction patterns collected at ambient conditions for NbSe2 and NbSe1.5Te0.5 showed a single phase with hexagonal crystal structure, with space group P63mmc. High-pressure X-ray diffraction measurements were performed at the Advanced Photon Source at Argonne National Laboratory to investigate structural stability up to …

Spectroscopic Investigation Of The Chemical And Electronic Properties Of Chalcogenide Materials For Thin-Film Optoelectronic Devices, Kimberly Horsley

UNLV Theses, Dissertations, Professional Papers, and Capstones

Chalcogen-based materials are at the forefront of technologies for sustainable energy production. This progress has come only from decades of research, and further investigation is needed to continue improvement of these materials.

For this dissertation, a number of chalcogenide systems were studied, which have applications in optoelectronic devices, such as LEDs and Photovoltaics. The systems studied include Cu(In,Ga)Se2 (CIGSe) and CuInSe2 (CISe) thin-film absorbers, CdTe-based photovoltaic structures, and CdTe-ZnO nanocomposite materials. For each project, a sample set was prepared through collaboration with outside institutions, and a suite of spectroscopy techniques was employed to answer specific questions about the system. These …

Equilibrium Speciation Of Select Lanthanides In The Presence Of Acidic Ligands In Homo- And Heterogeneous Solutions, Troy Robinson

UNLV Theses, Dissertations, Professional Papers, and Capstones

This dissertation explores lanthanide speciation in liquid solution systems related to separation schemes involving the acidic ligands: bis(2-ethylhexyl) phosphoric acid (HDEHP), lactate, and 8-hydroxyquinoline. Equilibrium speciation of neodymium (Nd³⁺ ), sodium (Na⁺ ), HDEHP, water, and lactate in the TALSPEAK liquid-liquid extraction system was explored under varied Nd³⁺ loading of HDEHP in the organic phase and through extraction from aqueous HCl and lactate media. System speciation was probed through vapor pressure osmometry, visible and Fourier Transform Infrared (FTIR) spectroscopy, ²² Na and ¹³ C labeled lactate radiotracer distribution measurements, Karl Fischer titrations, and equilibrium pH measurements. Distribution …

Synthesis, Extraction, Dissolution, And Voltammetry Of F-Species In A Room Temperature Ionic Liquid Solvent, Wendy Jacqueline Pemberton

UNLV Theses, Dissertations, Professional Papers, and Capstones

Room temperature ionic liquids (RTILs) are salts that are liquids from as low as -96 °C to up to 100 °C. RTILs are of high interest in many fields of study because of their negligible vapor pressure, high electrochemical stability, high conductivity, and wide electrochemical windows. These diverse solvents have recently been used in organic synthesis, as extraction solvents, and as electrochemical solvents. It is as a direct result of the multifunctional capabilities of these RTIL solvents that they are examined in this work. The ability to probe the chemistry of lanthanides and actinides is based on the unique properties …

Electrochemistry Of Technetium Analogues Rhenium And Molybdenum In Room Temperature Ionic Liquid, Pauline Nancy Serrano

UNLV Theses, Dissertations, Professional Papers, and Capstones

Rhenium was used as an analog for Technetium to study the electrochemical redox properties because the two elements share the same stable oxidation states in aqueous solutions. However, Tc-99 is radioactive and is not readily available for experimentation purposes. Molybdenum is also of interest because when Mo-99 is irradiated, the decay products are Tc-99m and Tc-99. Approximately 30% Tc-99m is eluted from the Mo columns for radiopharmaceutical use with the remaining Mo-99 source decaying to Tc-99 which is discarded as radioactive hospital waste. Currently there are no viable procedures for the reclamation of the radioactive Tc-99 from either fission streams …

Self-Assembling Organic Semiconductors With Tunable Electronic Properties Based On Novel Asymmetric Phenazine And Bisphenazine, Kyoungmi Jang

UNLV Theses, Dissertations, Professional Papers, and Capstones

Current demands in the area of organic semiconductors focus on both electronic and self-assembling properties. Particularly, one-dimensionally grown nanostructures of small organic semiconductors have drawn much attention for nanodevice fabrication. Self-assembly through various intermolecular interactions has been widely used to produce one-dimensionally grown nanostructures which can be induced by various methods such as rapid solution dispersion, a phase transfer method, vapor annealing, crystallization, and organogelation in conjunction with proper molecular design. Controlling the morphology of the nanostructures plays an important role in achieving desirable properties in optoelectronic device applications. While significant advancements have been made in developing molecular architectures for …

Chemical And Electronic Structure Of Surfaces And Interfaces In Compound Semiconductors, Sujitra Pookpanratana

UNLV Theses, Dissertations, Professional Papers, and Capstones

The interface formation between two different materials is important in applications for optoelectronic devices. Often, the success or performance of these devices is dependent on the formation of these heterojunctions. In this work, the surface and interfaces in such materials for optoelectronic devices are investigated by a suite of X-ray analytical techniques including X-ray photoelectron (XPS), X-ray excited Auger electron (XAES), and X-ray emission (XES) spectroscopies to provide novel insight.

For the group III-nitrides (e.g., AlxGa1-xN) used in many light emitting devices, a significant challenge exists to form an Ohmic contact. The electron affinities and band gaps of GaN and …

Characterization Of Iron Oxide Thin Films For Photoelectrochemical Hydrogen Production, Kyle Eustace Nelson George

UNLV Theses, Dissertations, Professional Papers, and Capstones

Solar energy is the most sustainable source of energy available. However, solar applications such as photovoltaic cells represent only a partial solution to weaning our dependence upon fossil fuels. Several methods of storing solar energy are currently being pursued, and chemical storage stands out as a promising option - combining design simplicity with high energy density, with hydrogen being particularly attractive because of its abundance and inherently clean nature. A monolithic Photoelectrochemical (PEC) device that produces hydrogen by electrolyzing water directly from sunlight has the benefit of utilizing "free" solar energy to drive the reaction.

Although α-Fe 2 O 3 …

Spectroscopic Investigation Of Palladium-Copper Bimetallic Systems For Pem Fuel Cell Catalysts, Timo Hofmann

UNLV Theses, Dissertations, Professional Papers, and Capstones

One of the main barriers to commercialization of polymer electrolyte membrane fuel cells systems is cost, which is largely due to the need of platinum (Pt)-containing catalysts. In this thesis we investigate bimetallic systems consisting of a base metal (copper) and a noble metal (palladium) that, as an alloy on the nanoscale, mimic the electronic properties that make Pt desirable as a catalyst.

We present a detailed investigation of the electronic structure of carbon-supported Pd/Cu nanoparticle catalysts, model bilayer thin film systems, alloys, and various metal reference samples. We have investigated the valence band structure of the catalysts using a …

Study Of Corrosion Of Materials In The Sulfur-Iodine Hydrogen Production Cycle, Thao Trung Ho

UNLV Theses, Dissertations, Professional Papers, and Capstones

Hydrogen is of great interest since the availability of traditional fossil fuels is in decline. Strictly speaking, hydrogen is not a primary source of energy but is an energy carrier, since energy typically must be used from another source (electricity, natural gas, coal, etc.) to produce it. Of hydrogen production techniques, the Sulfur-Iodine thermochemical water splitting process (S-I cycle), which was proposed by General Atomics (GA), is promising with its simplicity and high efficiency. Most of the chemicals are recycled except water. However, the S-I cycle operates in a harsh, corrosive environment in the presence of a mixture of iodine …

Investigation Of The Corrosion Of Steel By Lead-Bismuth Eutectic (Lbe) Using Scanning Electron Microscopy And X-Ray Photoelectron Spectroscopy, Daniel Koury

UNLV Theses, Dissertations, Professional Papers, and Capstones

Lead Bismuth Eutectic (LBE) has been proposed for use in programs for accelerator transmutation of waste. LBE is the leading candidate material as a spallation target and an option for the sub-critical blanket coolant. The corrosion of 316 and 316L stainless steels by LBE has been studied using UNLV's facilities for Scanning Electron Microscopy (SEM) and X-ray Photoelectron Spectroscopy (XPS). We have compared exposed and unexposed samples and studied the differences. Some amount of surface contamination is present on the samples and has been removed by ionbeam etching. The unexposed samples reveal typical stainless steel characteristics: a chromium oxide passivation …