Physical Sciences and Mathematics Commons^™

High-Pressure Studies On The Transition From Red Phosphorus To Black Phosphorus, Heng Xiang

Electronic Thesis and Dissertation Repository

Black phosphorus (BP) is a promising material in many research fields. However, the transition process from amorphous red phosphorus (ARP) is elusive and hence hinders large scale synthesis and applications. This work describes the application of the high-pressure method to study the transition process from ARP to BP.

In this thesis, the following three objectives were achieved: (1) to understand the mechanism of the transition, (2) to facilitate the synthesis of BP by taking the advantage of less pure ARP, (3) to propose new methods of synthesizing BP-based materials, such as the moderately oxidized BP and the black phosphorus/ amorphous …

Pressure Driven Electronic Band Gap Engineering In Tin(Iv)-O,N Compounds, Daniel Thomas Sneed

UNLV Theses, Dissertations, Professional Papers, and Capstones

The intrinsic link between long-range order, coordination geometry, and the electronic properties of a system must be understood in order to tailor function-specific materials. Although material properties are typically tailored using chemical dopants, such methods can cause irreversible changes to the structure, limiting the range of functionality. The application of high pressure may provide an alternative “clean” method to tune the electronic properties of semiconducting materials by tailoring their defect density and structure.

We have explored a number of optoelectronic relevant materials with promising characteristics, specifically Sn-(O,N) compounds which have been predicted to undergo pressure-mediated opening of their optical band …

Characterization And Computational Modelling For The Garnet Oxide Solid State Electrolyte Ta-Llzo, Colin A. Versnick

Electronic Thesis and Dissertation Repository

The all-solid-state-battery (ASSB) serves as a promising candidate for next generation lithium ion batteries for significant improvements in battery safety, capacity, and longevity. Of the material candidates researched to replace the conventionally used liquid electrolyte, the garnet oxide Ta-LLZO (Li_6.4La₃Zr_1.4Ta_0.6O₁₂) has received much attention thanks to its high chemical and electrochemical stability, and ionic conductivity which rivals that of liquid electrolytes. While much investigation has taken place regarding the electrochemical performance of Ta-LLZO, much less is known about the micromechanics, including microstructural characterization, stress and strain development, and material failure …

Studies Of Initial Growth Of Gan On Inn, Alaa Alnami

Graduate Theses and Dissertations

III-nitride materials have recently attracted much attention for applications in both the microelectronics and optoelectronics. For optoelectronic devices, III-nitride materials with tunable energy band gaps can be used as the active region of devices to enhance the absorption or emission. A such material is indium nitride (InN), which along with gallium nitride (GaN) and aluminum nitride (AlN) embody the very real promise of forming the basis of a broad spectrum, a high efficiency solar cell. One of the remaining complications in incorporating InN into a solar cell design is the effects of the high temperature growth of the GaN crystal …

Study Of Amorphous Boron Carbide And Hydrogenated Boron Carbide Materials Using Molecular Dynamics And Hybrid Reverse Monte Carlo, Rajan Khadka

MSU Graduate Theses

We present a computational study of amorphous boron carbide (a-B_xC) models using Molecular Dynamics (MD) studied with Stillinger-Weber (SW) and ReaxFF potential. The atomic structure factor (S(Q)), radial distribution function (RDF) and bond lengths comparison with other experimental and ab initio models shows that a random arrangement of icosahedra (B₁₂, B₁₁C) interconnected by chains (CCC, CBC) are present in a-B_xC. Afterward, Hybrid Reverse Monte Carlo (HRMC) technique is used to recreate a-B_xC structures. The existing SW potential parameters of Boron are optimized for the α-rhombohedral (Icosahedral B_{12 …}

Towards Completely Automated Glycan Synthesis, Matteo Panza

Dissertations

Carbohydrates are ubiquitous both in nature as biologically active compounds and in medicine as pharmaceuticals. Although there has been continued interest in the synthesis of carbohydrates, chemical methods require specialized knowledge and hence remain cumbersome. The need for development of rapid, efficient and operationally simple procedures has come to the fore. This dissertation focuses on the development of a fully automated platform that will enable both experts and non-specialists to perform the synthesis of glycans. Existing automated methods for the synthesis of oligosaccharides are highly sophisticated, operationally complex, and require significant user know-how. By contrast, high performance liquid chromatography (HPLC) …

First-Principles Simulations Of Materials Under Extreme Conditions, Kien Nguyen Cong

USF Tampa Graduate Theses and Dissertations

The investigation of materials at extreme conditions of high pressure and temperature (high-PT), has been one of the greatest scientific endeavors in condensed mater physics, chemistry, astronomy, planetary, and material sciences. Being subjected to high-PT conditions, materials exhibit dramatic changes in both atomic and electronic structure resulting in an emergence of exceptionally interesting phenomena including structural and electronic phase transitions, chemical reactions, and formation of novel compounds with never-previously observed physical and chemical properties. Although new exciting experimental developments in static and dynamic compression combined with new diagnostics/characterization methods allow to uncover new processes and phenomena at high P-T conditions, …

Fabrication And Characterization Of Electrical Energy Storage And Harvesting Energy Devices Using Gel Electrolytes, Belqasem Aljafari

USF Tampa Graduate Theses and Dissertations

Redox-active materials in the bulk of gel electrolytes are unquestionably holding the primary roles in developing energy harvesting and storage technology. Both technologies are necessary in order to cope with the current challenges of the environmental crises of global warming and finite non-renewable sources while the demand for energy modern societies have been speedily increased. One of the most challenges of making a hybrid device of energy conversion and storage is the cost of the fabrication process. Therefore, gel electrolyte-based materials with redox-active properties can potentially be a promising solution to improve the performance of electrochemical and photoelectrochemical devices for …

Thermo-Oxidative Degradation Of Hdpe Geomembranes: Effect Of Phenolic Antioxidant And Hindered Amine Light Stabilizer Concentrations, Yasin Kocak

USF Tampa Graduate Theses and Dissertations

High density polyethylene (HDPE) geomembrane is most common geomembrane which is mainly used for civil engineering applications. However, HDPE geomembrane loses its properties under oxidative degradation progress. This study aims to assess geomembranes which have different percentage of phenolic antioxidant and hindered amine light stabilizer (HALS) with under the six months of the thermal-oxidative degradation. The interactions between phenolic antioxidant, HALS and carbon black can affect the mechanical, physical and chemical properties. To monitor these properties, Differential Scanning Calorimetry (DSC), Fourier-transform Infrared Spectroscopy (FTIR), Thermogravimetric Analysis (TGA), Scanning Electron Microscopy coupled with Energy Dispersive X-ray spectroscopy (SEM/EDX), Melt Index tests, …

Top-Down And Bottom-Up Fabrication Of Key Components In Miniature Energy Storage Devices, Wenhao Li

Doctoral Dissertations

The advent of miniature electronic devices demands power sources of commensurate form factors. This spurs the research of micro energy storage devices, e.g., 3D microbatteries. A 3D microbattery contains nonplanar microelectrodes with high aspect ratio and high surface area, separated by a nanoscale electrolyte. The device takes up a total volume as small as 10 mm³, allowing it to serve on a chip and to provide power in-situ. The marriage of nanotechnology and electrochemical energy storage makes microbattery research a fascinating field with both scientific excitement and application prospect. However, successful fabrication of well-functioned key components …

Amorphous-Crystalline Brush Block Copolymers: Phase Behavior, Rheology And Composite Design, Gayathri Kopanati

Doctoral Dissertations

Bottlebrush block copolymers are polymers with chemically distinct polymer side chains grafted onto a common backbone. The unique architecture induced properties make these materials attractive for applications such as photonic materials, stimuli responsive actuators and drug delivery vehicles to name a few. This dissertation primarily investigates the phase transitions and rheological behavior of amorphous-crystalline bottlebrush brush block copolymers and their composites. The temperature induced phase behavior is investigated using time resolved synchrotron X-ray source. Irrespective of volume fraction and backbone length, the samples display strong segregation even at high temperatures (200 °C) and there is no accessible order-disorder transition in …

Polymeric Impulsive Actuation Mechanisms: Development, Characterization, And Modeling, Yongjin Kim

Doctoral Dissertations

Recent advances in the field of biomedical and life-sciences are increasingly demanding more life-like actuation with higher degrees of freedom in motion at small scales. Many researchers have developed various solutions to satisfy these emerging requirements. In many cases, new solutions are made possible with the development of novel polymeric actuators. Advances in polymeric actuation not only addressed problems concerning low degree of freedom in motion, large system size, and bio-incompatibility associated with conventional actuators, but also led to the discovery of novel applications, which were previously unattainable with conventional engineered systems. This dissertation focuses on developing novel actuation mechanisms …

Designing Ion-Containing Polymers With Controlled Structure And Dynamics, Joshua Enokida

Doctoral Dissertations

Ion-containing polymers are a unique class of materials for which strong electrostatic interactions dictate physical properties. By altering molecular parameters, such as the backbone chemical structure, the ion content, and the ion-pair identity, the structure and dynamics of these polymers can be altered. Further investigation of the molecular parameters that govern their structure-property relationships is critical for the future development of these polymeric materials. Particularly, the incorporation of ammonium-based counterions into these polymers offers a facile method to tune their electrostatic interactions and hydrophobicity. Applying this concept, a bulky dimethyloctylammonium (DMOA) counterion was used to modify the organic solubility of …

Novel Avenues Toward Controlling The Photophysical Properties Of Ultra-Small Silicon Quantum Dots, Mohammed Abdelhameed

Electronic Thesis and Dissertation Repository

Quantum dots (QDs) have attracted an increasing attention in the last decade over many conventional organic dyes. This is due to their unique optical properties including broad absorption spectra, high photostability, and size-tunable photoluminescence (PL). However, some toxicity concerns associated with traditional quantum dots have hindered their wide applicability. Interestingly, silicon quantum dots (SQDs) have been shown to be more advantageous than most of QDs thanks to their excellent biocompatibility and biodegradability, low cytotoxicity, and versatile surface functionalization capability. Thus, SQDs are promising candidates for various biological and biomedical applications such as bioimaging, biosensing, and photodynamic therapy. Unfortunately, only a …

Demonstration Of Visible And Near Infrared Raman Spectrometers And Improved Matched Filter Model For Analysis Of Combined Raman Signals, Alexander Matthew Atkinson

Electrical & Computer Engineering Theses & Dissertations

Raman spectroscopy is a powerful analysis technique that has found applications in fields such as analytical chemistry, planetary sciences, and medical diagnostics. Recent studies have shown that analysis of Raman spectral profiles can be greatly assisted by use of computational models with achievements including high accuracy pure sample classification with imbalanced data sets and detection of ideal sample deviations for pharmaceutical quality control. The adoption of automated methods is a necessary step in streamlining the analysis process as Raman hardware becomes more advanced. Due to limits in the architectures of current machine learning based Raman classification models, transfer from pure …

Nonlinear Characterizing Of A New Titanium Nitride On Aluminum Oxide Metalens, Michael A. Cumming

Theses and Dissertations

A sample metalens generated from Titanium Nitride deposited onto Aluminum Oxide was designed to focus at 10 microns with a beam centered at 800nm, and when analyzed with high intensity illumination was found to have a focal length of 9.650 ±.003µm at an intensity of 16.93[MW/cm² ]. Analyzing this change by comparing it to a Fresnel Lens’ physics shows that for this lens, the effective nonlinear index of refraction is certainly greater than the nonlinear index of just Titanium Nitride itself, at −1.6239 × 10⁻¹⁵[m²/W] compared to the materials −1.3 × 10⁻¹⁵[m^{2 …}

Shape-Controlled Nanoparticles As Effective Catalysts For Proton Exchange Membrane (Pem) Fuel Cells, Ali Feizabadi

Electronic Thesis and Dissertation Repository

Polymer electrolyte membrane fuel cell (PEMFC), is considered a promising candidate for the next generation power sources in transportation, stationary and portable applications. However, oxygen reduction reaction (ORR), one of the key reactions occurring on PEMFC is kinetically slow; this has limited performance and further advancement in this kind of fuel cells. Thus, improving the PEMFC efficiency requires a thorough understanding of the ORR mechanism on the desired catalyst. To address the above-mentioned demands, the scope of this thesis is focused on the fundamental understanding of facet-controlled nanoparticles, metal-support interactions, and bimetallic platinum catalysts, utilizing synchrotron-based X-ray absorption, X-ray photoelectron …

Self-Assembly Of Conducting Polymer Nano- And Microstructures For Energy Storage, Luciano Matteo Santino

Arts & Sciences Electronic Theses and Dissertations

Plastics are materials composed of many long chains of molecules with repeating subunits; strong interactions between neighboring molecules lead to the material used throughout the world. Plastics are commonly thought to be insulating, in stark contrast to the conductivity of metals. However, certain polymer structures were discovered to exhibit semiconducting properties, the subject of the Nobel Prize in Chemistry in 2000. Conducting polymers have a unique molecular structure with an electronically conjugated backbone, allowing electrons to freely travel both across the chain and in between chains. This work focuses on controlling the kinetics of the reaction between the vapors of …

General Nonlinear-Material Elasticity In Classical One-Dimensional Solid Mechanics, Ronald Joseph Giardina Jr

University of New Orleans Theses and Dissertations

We will create a class of generalized ellipses and explore their ability to define a distance on a space and generate continuous, periodic functions. Connections between these continuous, periodic functions and the generalizations of trigonometric functions known in the literature shall be established along with connections between these generalized ellipses and some spectrahedral projections onto the plane, more specifically the well-known multifocal ellipses. The superellipse, or Lam\'{e} curve, will be a special case of the generalized ellipse. Applications of these generalized ellipses shall be explored with regards to some one-dimensional systems of classical mechanics. We will adopt the Ramberg-Osgood relation …

Increasing The Functionality Of Additive Manufacturing Through Atmospheric Microplasma And Nanotechnology, Alexander Jon Ulrich

Doctoral Dissertations

Additive Manufacturing (AM) has been changing the manufacturing landscape for the last 20 years. As the interest and demand for both polymer and metal-based 3D printing has grown, the materials and machines used have increased in capabilities. Despite the growth and advancement, there are still a large number of improvements that can be made to add functionality to 3D printers. Metal AM, a subcategory of 3D printing, has garnered much attention among industrial applications with large companies such as General Electric trying to implement the technology to increase innovative designs for motors. Some of the limitations on AM have to …

Optimizing Self-Healing Wind Turbine Blades Utilizing Dicyclopentadiene Infused Vascular Networks, Giovanni Lewinski

Theses and Dissertations

Self-healing wind turbine blades can reduce costs associated with maintenance, repair, and energy compensation. Self-healing is the ability to sustain and recover from damage autonomously. The self-healing presented in this paper uses the reaction of two agents Dicyclopentadiene, DCPD, and Grubbs’ first-generation catalyst, henceforward known as a catalyst to fuel this recovery. DCPD is housed as a liquid isolated from the catalyst until a damaging event occurs, causing the two agents to mix and solidify to form the thermoset Polydicyclopentadiene, PDCPD. We discuss the efforts made to optimize the self-healing properties of wind turbine blades and provide new systems to …

Growth Of Indium Nitride Quantum Dots By Molecular Beam Epitaxy, Steven P. Minor

Graduate Theses and Dissertations

Over the last decade, the evolution of the global consciousness in response to decreasing environmental conditions from global warming and pollution has led to an outcry for finding new alternative/clean methods for harvesting energy and determining ways to minimize energy consumption. III-nitride materials are of interest for optoelectronic and electronic device applications such as high efficiency solar cells, solid state lighting (LEDs), and blue laser (Blu-ray Technology) applications. The wide range of direct band gaps covered by its alloys (0.7eV-6.2eV) best illustrates the versatility of III-nitride materials. This wide range has enabled applications extending from the ultraviolet to the near …

Double-Network Materials Via Frontal Polymerization & Supercritical Co2 Processing, Matthew Joseph Lampe

Doctoral Dissertations

This dissertation presents work focused on producing materials in non-equilibrium states by taking advantage of novel processing techniques. First, epoxy-based resins which can undergo radically promoted, cationic, thermal, frontal polymerization are investigated for their potential use as adhesives. These resins are found to be capable of sustaining propagating polymerization fronts between several different substrate materials, resulting in high levels of adhesion in some cases. In addition, a similar frontal resin was developed that can undergo sequential gelation and frontal polymerization. The gels are formed by radically crosslinking acrylate monomers within the epoxy resin. These gels can then be manipulated, and …

Northeastern Species In Hybrid Cross Laminated Timber, Hamid Kaboli

Doctoral Dissertations

Known in the building industry throughout the world, Cross Laminated Timber (CLT) is a massive timber building material with outstanding structural, fire, and seismic properties. CLT is a cost-competitive, sustainable construction material is a good candidate as a substitute material for concrete, masonry, and steel, in mid-rise and high-rise buildings. CLT is perpendicular layers of dimensional lumbers usually laminated together and forming a massive structural panel. This dissertation explores the viability of utilizing Massachusetts grown Eastern Hemlock and Eastern White Pine in CLT panels as pure or in conjunction with other high-value wood products. 59% of Massachusetts’ lands are covered …

Investigation Of Fundamental Principles Of Rigid Body Impact Mechanics, Khalid Alluhydan

Mechanical Engineering Research Theses and Dissertations

In impact mechanics, the collision between two or more bodies is a common, yet a very challenging problem. Producing analytical solutions that can predict the post-collision motion of the colliding bodies require consistent modeling of the dynamics of the colliding bodies. This dissertation presents a new method for solving the two and multibody impact problems that can be used to predict the post-collision motion of the colliding bodies. Also, we solve the rigid body collision problem of planar kinematic chains with multiple contacts with external surfaces.

In the first part of this dissertation, we study planar collisions of Balls and …

Implementation Of Multivariate Artificial Neural Networks Coupled With Genetic Algorithms For The Multi-Objective Property Prediction And Optimization Of Emulsion Polymers, David Chisholm

Master's Theses

Machine learning has been gaining popularity over the past few decades as computers have become more advanced. On a fundamental level, machine learning consists of the use of computerized statistical methods to analyze data and discover trends that may not have been obvious or otherwise observable previously. These trends can then be used to make predictions on new data and explore entirely new design spaces. Methods vary from simple linear regression to highly complex neural networks, but the end goal is similar. The application of these methods to material property prediction and new material discovery has been of high interest …

Nano Fab Lab 63, Brian K. Deemer, Josh Clemons, Nick Brodine, Delaney Fitzsimmons

Mechanical Engineering

Lawrence Livermore National Laboratories (LLNL) has several steps in the production process for ceramic nanofiber tubes that they would like to improve - electrospinning, cutting, rolling, sealing and heat treating. We undertook the challenge to deliver LLNL with a semi-automated process that efficiently integrates the steps of cutting, rolling, and sealing to save time and improve control over end dimensions. In this document, we discuss the technical background of the manufacturing steps currently followed to create nanofiber tubes, identify which steps are incorporated in our prototype and explain how they will interface with one another, define the design requirements, present …

Supercapacitors With Gate Electrodes, Tazima Selim Chowdhury

Dissertations

A new approach to improve the capacitance of supercapacitors (SC) is proposed in this study. A typical SC is composed of an anode and a cathode; a separator in between them assures an unintentional discharge of the capacitor. The study focuses on a family of structured separators, either electronically active or passive which are called gates. An active structured separator layer has been fabricated and analyzed. The structured separator has characteristics of electrical diode and is fabricated out of functionalized carbon nanotubes (CNT). Improvement of the overall capacitance of SC, equipped with either active or passive structured separators demonstrated a …

N8- Polynitrogen Stabilized On Carbon-Based Supports As Metal-Free Electrocatalyst For Oxygen Reduction Reaction In Fuel Cells, Zhenhua Yao

Dissertations

The sluggish oxygen reduction reaction (ORR) kinetics at the cathode is one of the key factors limiting the performance of polymer electrolyte membrane fuel cell (PEMFC). Platinum-based materials are the most widely studied catalysts for this ORR reaction while their large-scale practical application in fuel cells is hindered due to their scarcity and low stability. Therefore, highly active, low cost and robust non-Pt catalysts are being developed to overcome the drawbacks. Recently, a novel polynitrogen N8- (PN) stabilized on multiwall carbon nanotube (MWNT) was synthesized under ambient condition for the first time by our group and demonstrated high ORR activities. …

Surface-Enhanced Raman Detection Of Glucose On Several Novel Substrates For Biosensing Applications, Laila Saad Alqarni

Dissertations

The small normal Raman cross-section of glucose is considered to be a major challenge for its detection by Surface Enhanced Raman Spectroscopy (SERS) for medical applications. These applications include blood glucose level monitoring of diabetic patients and evaluation of patients with other medical conditions, since glucose is a marker for many human diseases. This dissertation focuses on Surface-Enhanced Raman Scattering primarily for the detection of glucose. Some experiments also are carried out for the detection of the corresponding enzyme glucose oxidase that is used in electrochemical glucose sensors and in biofuel cells. This project explores the possibility of utilizing Surface …