Physical Sciences and Mathematics Commons^™

Study Of Grain Growth In Single-Phase Polycrystals, Pawan Vedanti

Wayne State University Dissertations

Materials with random microstructure are characterized by additional thermodynamic parameters, entropy and temperature of microstructure. It has been argued that there is one more law of thermodynamics: entropy of microstructure decays in isolated systems. This assertion has been checked experimentally for the process of grain growth which showed that entropy of grain structure decays indeed as expected. The equation of state for microstructure entropy has also been studied. In general, entropy of grain microstructure is expected to be a function of grain structure energy and the average grain size. Our experiments suggest that in fact, the equation of state degenerates …

Characterization, Modeling, And Thermal Management Of High-Performance Lithium Batteries, Minjun Bae

Wayne State University Theses

Lithium-ion (Li-ion) batteries, as one of the most advanced commercial rechargeable batteries, play a crucial role in modern society as they are extensively used in portable electronic devices. Nevertheless, the limited electrochemical performance and poor thermal management systems of Li-ion batteries have hindered the expansion of their future applications. In search of alternative electrode materials to develop a battery with higher electrochemical performance, lithium (Li) metal has attracted much attention as an ideal alternative anode material due to its high specific capacity and lowest redox potential. However, needle-like Li dendritic growth causes severe safety concerns and thus prohibits practical applications …

Tunable Refractive Index Through Spatially Modified Nanoparticle Films For Long-Range Spr Biosensing Applications, Stephen Joshua Binderup

Graduate Research Theses & Dissertations

Despite optics and refraction being among the oldest scientific principles, material limitations have prevented scientists from taking full advantage of the potential this technology holds. Indeed, films with designer optical properties have potential for use in exotic cloaking architectures, advanced waveguides, and precise optical biosensors. This thesis focuses on the fabrication methodology for making thin films with refractive index tuned to a desired value through self-assembly of amorphous nanoparticle films made of organosilicate materials. The inclusion of a slowly evaporating polymer phase along with the organosilicate nanoparticles results in nanopores formed within the film, which effectively reduce the film’s refractive …

Fundamental Study Of Supported Metal Catalysts Prepared By Metal In Lithium Solution For Energy Science, Haiping Xu

Graduate Research Theses & Dissertations

Electrochemical carbon dioxide reduction reaction (CO2RR) is a promising technique for energy conversion and storage from intermittent electricity sources (ie. wind and solar). By coupling electrochemical CO2 reduction (CO2R) to a renewable energy source atmospheric CO2 could be converted back into a fuel such as ethanol, or a commodity chemical such as ethanol or acetic acid. These products could then be consumed for energy or used to generate more valuable chemical products effectively removing CO2 from the atmosphere. To commercialize this process, it is highly desired to prepare catalysts that selectively reduce CO2 at low overpotential with long durability. Research …

Multi-Component Material For Solar Energy Conversion And Fundamentals Of Lead Acid Batteries, Crystal Ferels

Graduate Research Theses & Dissertations

Synthesis of complex inorganic materials is desirable because their complex composition allows more degrees of freedom and tunability, whose properties differ from their parent components. As an expansion on this concept, we synthesized a quinary compound Ce3FeWS3O6, using a molten flux method and a solvothermal method. The compound crystallizes into a hexagonal crystal system with space group P63/m. Its electric partition shows an anion with the form [(Ce3+)3W6+(S2-)3(O2-)6]3- forcing the transition metal Fe3+ state and leaving no conduction electrons, making the material a semiconductor. This compound is the right candidate as photoelectric material capable of absorbing photons from the solar …

Shape Tuning Of Silicon Nano-Tip Arrays Through Reactive Ion Etching For Cold Field Emission, Giridhar Tulasi Ram Sankabathula

Graduate Research Theses & Dissertations

Large area silicon nano-tip arrays have been predominantly used as cold cathode electron sources in the wide range of field emission applications. Various fabrication methodologies have been developed over the decades to obtain sharp-pointed field emitters. In this thesis, we mainly emphasized on reproducing high aspect ratio field emitters and to study their surface topographical changes encountered through reactive ion etching. A discrete set of high-density field emitters have been fabricated over the large area surfaces through a three-step nanofabrication process. The surface curvatures of the obtained emitter tips are finely tuned with multiple oxidation cycles to achieve a tip’s …

Macro - And Microstructure Evaluation And Field Applications Of Concrete With Recycled Glass Pozzolan, Marija Krstic

Dissertations and Theses

Concrete is the most used material in the world, second only to water. Conventional concrete is produced with Portland cement (PC). The production of cement is an energy intensive operation that has raised significant environmental concerns, since one ton of cement generates an equal ton of CO₂. In the USA about 90 million tons of cement are used annually, with 3 million tons used in New York. Most contemporary concrete applications for buildings and infrastructure use high-performance concrete (HPC) mixtures which are produced by replacing a percentage of cement with supplementary cementitious materials (SCMs), consisting mainly of fly-ash …

Investigation Of Iron Doped Gallium Oxide (Ga-Fe-O) System: Structure Property Relationship And Performance Evaluation For Optical And Catalytic Applications, Swadipta Roy

Open Access Theses & Dissertations

From September 2012 to May 2015, a phenocam monitored the seaward edge of a protected mangrove forest. Calculated GCC revealed seasonal greening patterns of a mangrove species, Rhizophoa apiculata, and an overall increase in the GCC, suggesting mangrove expansion. In comparing temperature and precipitation effects, it was found that this particular mangrove species had a greening optima at temperatures between 28°C and 28.5°C, and greening and canopy development response lag time of 10 weeks in response to precipitation. Tree saplings were monitored and showed to grow by 50%, mostly during a three month period during the rainy season. The establishment …

Development Of Software Tools And Experimental In Situ Electron Spin Resonance For Characterizing The Magnetic And Electrocatalytic Properties Of Transition Metal Chalcogenide Crystals, Jose Armando Delgado

Open Access Theses & Dissertations

Studying the magnetic properties and crystal defects of transition metal chalcogenide crystals is of paramount importance for utilizing them for next generation spintronics devices and hydrogen evolution reaction catalysts. Hydrothermally grown transition metal chalcogenide nanocrystals (MoS2, Ru2S3, Rh2S3, Co2S8) were chosen as catalysts for the hydrogen evolution reaction due to their low dimensionality and previous utilization as catalysts for hydrodesulfurization. The relationship between crystal defect sites and catalytic activity must be discerned to maximize the efficiency of hydrogen production during the hydrogen evolution reaction. ESR spectroscopy was utilized as a spin sensitive technique to study the defects and local changes …

Thermoelectric Porous Mof Based Hybrid Materials, Engelbert Redel, Helmut Baumgart

Electrical & Computer Engineering Faculty Publications

Porous hybrid materials and MOF (Metal-Organic-Framework) films represent modern designer materials that exhibit many requirements of a near ideal and tunable future thermoelectric (TE) material. In contrast to traditional semiconducting bulk TE materials, porous hybrid MOF templates can be used to overcome some of the constraints of physics in bulk TE materials. These porous hybrid systems are amenable for simulation and modeling to design novel optimized electron-crystal phonon-glass materials with potentially very high ZT (figure of merit) numbers. Porous MOF and hybrid materials possess an ultra-low thermal conductivity, which can be further modulated by phonon engineering within their complex porous …

Magnetism In Γ-Fesi2 Nanostructures: A First Principles Study, Sahil Dhoka

Dissertations, Master's Theses and Master's Reports

First-principles calculations are performed on γ-FeSi₂ nanostructures grown on Si (111) and (001) substrate. An attempt to explain the origin of emergent magnetic properties of the metastable gamma phase of iron di-silicide (γ-FeSi₂) is made, which show ferromagnetic behavior on nanoscale, unlike its possible bulk form. Many papers try to explain this magnetism from factors like bulk, epitaxial strain, interface, surface, edges, and corners but doesn’t provide an analytical study for these explanations. Density functional theory is used to analyze the magnetic effects of these factors. The results for the epitaxial structures show no magnetic behavior for …

Effects Of Hole Transporting Layers And Surface Ligands On Interface Energetics And Photovoltaic Performance Of Methylammonium Lead Iodide Perovskites, So Min Park

Theses and Dissertations--Chemical and Materials Engineering

Organic metal halide perovskites are promising materials for various optoelectronic device applications such as light emitting diodes (LED) and photovoltaic (PV) cells. Perovskite solar cells (PSCs) have shown dramatic increases in power conversion efficiency over the previous ten years, far exceeding the rate of improvement of all other PV technologies. PSCs have attracted significant attention due to their strong absorbance throughout the visible region, high charge carrier mobilities, color tunability, and ability to make ultralight weight devices. However, organic metal halide perovskites still face several challenges. For example, their environmental stability issue must be overcome to enable widespread commercialization. Meeting …

Effects Of Oxygen Modification On The Structural And Magnetic Properties Of Highly Epitaxial La0.7sr0.3mno3 (Lsmo) Thin Films, Shalini Kumari, Navid Mottaghi, Chih-Yeh Huang, Robbyn Trappen, Ghadendra Bhandari, Saeed Yousefi, Guerau Cabrera, Mohindar S. Seehra, Mikel B. Holcomb

Faculty & Staff Scholarship

La0.7Sr0.3MnO3, a strong semi-metallic ferromagnet having robust spin polarization and magnetic transition temperature (TC) well above 300 K, has attracted significant attention as a possible candidate for a wide range of memory, spintronic, and multifunctional devices. Since varying the oxygen partial pressure during growth is likely to change the structural and other physical functionalities of La0.7Sr0.3MnO3 (LSMO) films, here we report detailed investigations on structure, along with magnetic behavior of LSMO films with same thickness (~30 nm) but synthesized at various oxygen partial pressures: 10, 30, 50, 100, 150, 200 and 250 mTorr. The observation of only ( …

Synthesis Of Graphene Using Plasma Etching And Atmospheric Pressure Annealing: Process And Sensor Development, Andrew Robert Graves

Graduate Theses, Dissertations, and Problem Reports

Having been theorized in 1947, it was not until 2004 that graphene was first isolated. In the years since its isolation, graphene has been the subject of intense, world-wide study due to its incredibly diverse array of useful properties. Even though many billions of dollars have been spent on its development, graphene has yet to break out of the laboratory and penetrate mainstream industrial applications markets. This is because graphene faces a ‘grand challenge.’ Simply put, there is currently no method of manufacturing high-quality graphene on the industrial scale. This grand challenge looms particularly large for electronic applications where the …

The Synthesis Of Pb2sr2sm1-Xcaxcu3o8 And Characterization Of Its Structural And Superconducting Properties., Deblina Das

Graduate Research Theses & Dissertations

Superconducting lead-based cuprate materials of the 2213 structural type, Pb2Sr2MCu3O8 (M=Sm1-xCax, Y1-xCax, Er1-xCax and Yb1-xCax), were synthesized and characterized using x-ray powder diffraction and the Rietveld structural refinements method. Pb2Sr2Sm1-xCaxCu3O8 single crystals were grown by an optimized flux method using various combinations of PbO/PbF2 solvents. Samples with different Sm/Ca ratios were investigated for their superconducting properties. Magnetic measurements reveal the presence of a transition at 120K. Preliminary x-ray diffuse scattering experiment at the Advanced Photon Source of Argonne National Laboratory demonstrates the high quality of one of our crystals and the presence of rod-like diffuse scattering connecting the Bragg peaks …

Carbon Oxidation At The Atomic Level: A Computational Study On Oxidative Graphene Etching And Pitting Of Graphitic Carbon Surfaces, Simon Schmitt

Theses and Dissertations--Mechanical Engineering

In order to understand the oxidation of solid carbon materials by oxygen-containing gases, carbon oxidation has to be studied on the atomic level where the surface reactions occur. Graphene and graphite are etched by oxygen to form characteristic pits that are scattered across the material surface, and pitting in turn leads to microstructural changes that determine the macroscopic oxidation behavior. While this is a well-documented phenomenon, it is heretofore poorly understood due to the notorious difficulty of experiments and a lack of comprehensive computational studies. The main objective of the present work is the development of a computational framework from …

Gravity-Drawing Flexible Silicone Filaments As Fiber Optics And Model Foldamers, Katherine Snell

CMC Senior Theses

Here, we present a method of gravity-drawing polydimethylsiloxane (PDMS) silicone fibers with application as fiber optics and as model foldamers. Beginning as a viscous liquid, PDMS is cured using heat until its measured viscosity reaches 4000 mPa•s. The semi-cured elastomer is then extruded through a tube furnace to produce thin (diameters on the order of hundred micrometers) filaments with scalable lengths. PDMS is biocompatible, gas-permeable, flexible, and hydrophobic. Additionally, the PDMS surface hydrophobicity can be modified via UV exposure, O2 plasma, and corona discharge. We demonstrate the patternibility (i.e patterns of hydrophobicity) of PDMS fibers, adding complexity to potential foldamer …

A Theoretical And Experimental Study Of Charge Transport In Organic Thermoelectric Materials And Charge Transfer States In Organic Photovoltaics, Ashkan Abtahi

Theses and Dissertations--Physics and Astronomy

Applications of organic electronics have increased significantly over the past two decades. Organic semiconductors (OSC) can be used in mechanically flexible devices with potentially lower cost of fabrication than their inorganic counterparts, yet in many cases organic semiconductor-based devices suffer from lower performance and stability. Investigating the doping mechanism, charge transport, and charge transfer in such materials will allow us to address the parameters that limit performance and potentially resolve them. In this dissertation, organic materials are used in three different device structures to investigate charge transport and charge transfer. Chemically doped π-conjugated polymers are promising materials to be used …

Time-Dependent Reliability Framework For Durability Design Of Frp Composites, Rajneesh Kumar Bharil

Graduate Theses, Dissertations, and Problem Reports

The life-cycle performance, durability, and aging characteristics of Fiber Reinforced Polymer (FRP or Structural Composites) have been of keen interest to the engineers engaged in the FRP design, construction, and manufacturing. Unlike conventional construction materials such as steel and concrete, the design guidelines to account for the aging of FRP are somewhat scattered or not available in an approved or consistent format. Loss of strength over time or aging of any structural material should be of concern to engineers as the in-service lifespan of many engineering structures is expected to exceed 100 years. Use of durability strength-reduction factors or factors …

Studying The Effects Of Various Process Parameters On Early Age Hydration Of Single- And Multi-Phase Cementitious Systems, Rachel Cook

Doctoral Dissertations

”The hydration of multi-phase ordinary Portland cement (OPC) and its pure phase derivatives, such as tricalcium silicate (C₃S) and belite (ß-C₂S), are studied in the context varying process parameters -- for instance, variable water content, water activity, superplasticizer structure and dose, and mineral additive type and particle size. These parameters are studied by means of physical experiments and numerical/computational techniques, such as: thermodynamic estimations; numerical kinetic-based modelling; and artificial intelligence techniques like machine learning (ML) models. In the past decade, numerical kinetic modeling has greatly improved in terms of fitting experimental, isothermal calorimetry to kinetic-based modelling …

Transition Metal Chalcogenide Hybrid Systems As Catalysts For Energy Conversion And Biosensing, Siddesh Umapathi

Doctoral Dissertations

"Generation of hydrogen and oxygen through catalyst-aided water splitting which has immense applications in metal air batteries, PEM fuel cells and solar to fuel energy production, has been one of the critical topics in recent times. The state of art oxygen evolution reaction (OER), oxygen reduction reaction (ORR), hydrogen evolution reaction (HER) catalysts are mostly comprised of precious metals. The current challenge lies in replacing these precious metal-based catalysts with non-precious earth-abundant materials without compromising catalytic efficiency.

This research explores mixed metal selenides containing Fe-Ni, Fe-Co and RhSe which were hydrothermally synthesized and/or electrodeposited and tested for OER and ORR …

Enhanced Electrochemical Performance Of Li-Ion Battery Cathodes By Atomic Layer Deposition, Yan Gao

Doctoral Dissertations

”Li-ion battery now plays an irreplaceable role in supplying green and convenient energy. In this work, atomic layer deposition (ALD) was used to modify Li-ion battery cathode particles for performance enhancement.

An ultrathin and conductive CeO₂ ALD film was deposited on Li-rich layered cathode particles, of which the specific capacity and cyclic stability were significantly improved. On the same cathode particles, FeO_x ALD and post-annealing resulted in a stable and conductive surface spinel phase to improve the performance.

Synergetic TiN coating and Ti doping were performed on a LiFePO₄ (LFP) cathode and extended its cycle life. The …

Electron Tunneling And X-Ray Photoelectron Spectoscopy Studies Of The Superconductiong Properties Of Nitrogen-Doped Niobium Resonator Cavities, Eric M. Lechner, Basu Dev Oli, Junki Makita, Gianluigi Ciovati, Alex Gurevich, Maria Iavarone

Physics Faculty Publications

We use scanning tunneling microscopy (STM) and spectroscopy (STS), and x-ray photoelectron spectroscopy (XPS) to investigate the effect of nitrogen doping on the surface electronic and chemical structures of cutouts from superconducting Nb radio-frequency cavities. The goal of this work is to get insights into the fundamental physics and materials mechanisms behind the striking decrease of the surface resistance with the radio-frequency magnetic field, which has been observed on N-doped Nb cavities. Our XPS measurements reveal significantly more oxidized Nb 3d states and a thinner metallic suboxide layer on the N-doped Nb surfaces, which is also confirmed by tunneling spectroscopy …

Observation Of Reduced Thermal Conductivity In A Metal-Organic Framework Due To The Presence Of Adsorbates, Hasan Babaei, Mallory E. Decoster, Minyoung Jeong, Zeinab M. Hassan, Timur Islamoglu, Helmut Baumgart, Alan J.H. Mcgaughey, Engelbert Redel, Omar K. Farha, Patrick E. Hopkins, Jonathan A. Malen, Christopher E. Wilmer

Electrical & Computer Engineering Faculty Publications

Whether the presence of adsorbates increases or decreases thermal conductivity in metal-organic frameworks (MOFs) has been an open question. Here we report observations of thermal transport in the metal-organic framework HKUST-1 in the presence of various liquid adsorbates: water, methanol, and ethanol. Experimental thermoreflectance measurements were performed on single crystals and thin films, and theoretical predictions were made using molecular dynamics simulations. We find that the thermal conductivity of HKUST-1 decreases by 40 – 80% depending on the adsorbate, a result that cannot be explained by effective medium approximations. Our findings demonstrate that adsorbates introduce additional phonon scattering in HKUST-1, …

Gold/Qds-Embedded-Ceria Nanoparticles: Optical Fluorescence Enhancement As A Quenching Sensor, Nader Shehata, Effat Samir, Ishac Kandas

Electrical & Computer Engineering Faculty Publications

This work focuses on improving the fluorescence intensity of cerium oxide (ceria) nanoparticles (NPs) through added plasmonic nanostructures. Ceria nanoparticles are fluorescent nanostructures which can emit visible fluorescence emissions under violet excitation. Here, we investigated different added plasmonic nanostructures, such as gold nanoparticles (Au NPs) and Cadmium sulfide/selenide quantum dots (CdS/CdSe QDs), to check the enhancement of fluorescence intensity emissions caused by ceria NPs. Different plasmonic resonances of both aforementioned nanostructures have been selected to develop optical coupling with both fluorescence excitation and emission wavelengths of ceria. In addition, different additions whether in-situ or post-synthesis have been investigated. We found …

Synthesis Of Metal Oxide Surface And Interface Arrays By A Combined Solid-Liquid- Vapor/Vapor-Liquid-Solid Approach, Alexandra J. Riddle

Theses and Dissertations--Chemistry

This project was motivated by an in situ heating experiment in the transmission electron microscope (TEM) in which gold (Au) nanoparticles were observed to dissolve tin dioxide (SnO2) nanowires (NWs) under vacuum. The explanation for this observation was that the high-temperature and low-pressure environment of the TEM caused the reverse reaction of the well-known vapor-liquid-solid (VLS) method commonly used to grow NWs. In the VLS process, a metal catalyst absorbs reactant vapor until it becomes supersaturated. The precipitation of the NW occurs at the liquid-solid interface, which ceases when there is no longer reactant vapor, and the diameter of the …

Interfaces In Lead-Free Tin Perovskite Photovoltaics: An Investigation Of Energetics, Ion Mobility, Surface Modification, And Performance, Alex Boehm

Theses and Dissertations--Chemistry

Halide perovskites have generated tremendous interest as low-cost semiconductors for optoelectronics, such as photovoltaics, lasers, and light emitting diodes due to their extraordinary optical and transport properties. Perovskite photovoltaics in particular have demonstrated a meteoric rise in power conversion efficiencies and drawn considerable interest as a next-generation solar energy technology. The rapid development has centered around lead-based derivatives, and concerns regarding the toxicity of lead has sparked interest in low toxicity and more environmentally friendly perovskite derivatives. In this regime tin (Sn) is regarded as a prominent alternative owing to the ideal bandgap and reduced toxicity exhibited by Sn-halide perovskites. …