Chemistry Commons^™

Corrosion Of Aluminum Current Collector In Cost Effective Rechargeable Lithium-Ion Batteries, Shengyi Li

Theses and Dissertations

Rechargeable lithium ion batteries (LIB) have been widely used as commercial energy storage systems for portable equipment, electronic devices and high power applications (e.g. electronic vehicles). One issue with the commercialized LIB is that expensive, highly toxic and flammable organic solvents are used in the electrolyte and the fabrication process of electrodes. The toxic organic based solvents increase the production cost and lead to significant safety concerns in the event of a battery overcharge or short circuit. The recent development of “green manufacturing” technology allows manufacturers to replace the organic solvents used in the cathode coating process by aqueous based …

Structure-Property Relationships Of Polyisobutylene-Block-Polyamide Thermoplastic Elastomers, Morgan Dunn Heskett

Master's Theses

Thermoplastic elastomers (TPEs) are a class of polymer fit for a wide variety of applications due to their customizability. In the synthesis of these types of materials, an elastically-performing polymer, deemed the “soft block,” is combined with a stiffer “hard block” polymer, each of which can be selected based on their own specific properties in order to achieve desired material behavior in the final copolymer. Recently, the use of polyisobutylene as a soft block in combination with a polyamide hard block has been investigated for use in TPE synthesis. While the material showed some promising behavior, many properties were still …

Role Of The Inner Shell Architecture On The Various Blinking States And Decay Dynamics Of Core-Shell And Core-Multishell Quantum Dots, Pooja Bajwa

Graduate Theses and Dissertations

Colloidal semiconductor nanocrystals (quantum dots, QDs) have received much attention in recent years due to their uniquely size-tunable properties leading to a number of promising applications. Some of their most popular applications include their use as fluorescent probes in biology, as electro-optical components and in photovoltaic devices. CdSe-based QDs are particularly important because of their ease of synthesis, high photoluminescence quantum yields (PL QYs) across the whole visible spectrum and their photostabilty. Shelling of core QDs is usually carried out to improve their optical properties, minimize outer environmental effects on their properties, and avoid toxic element exposure to the environment. …

Design And Synthesis Of Dynamic Covalent Polymer Scaffolds With Controlled Architectures, Emily Annette Hoff

Dissertations

The design and synthesis of functional, controlled polymer architectures is essential to the development of new materials with precise and tailorable properties or applications. The work described in this dissertation focuses on the development of controlled polymer architectures with dynamic linkages for the design of multifunctional materials and surfaces via robust, efficient, and stimuli-responsive strategies.

In Chapter III, a post-polymerization modification strategy based on ambient temperature nucleophilic chemical deblocking of polymer scaffolds bearing N-heterocycle blocked isocyanate moieties is reported. Room temperature RAFT polymerization of three azole-N-carboxamide methacrylates, including 3,5-dimethyl pyrazole, imidazole, and 1,2,4-triazole derivatives, afforded reactive polymer scaffolds …

Molecular Tetrapods For Optoelectronic Applications, Jianzhong Yang

Chemistry and Chemical Biology ETDs

In this dissertation, several molecular tetrapods were synthesized for optoelectronic applications. In the first two sections, two tetrapodal breakwater-like small molecules: SO and SFBTD were synthesized and characterized. Absorption, X-ray scattering and differential scanning calorimetry experiments indicate crystalline nature of these compounds but slow crystallization kinetics. Solar cells employing SO or SFBTD and phenyl-C₆₁-butyric acid methyl ester (PCBM) were fabricated and evaluated. Relatively low performance was obtained mainly due to the lack of appropriate phase separation, which was caused by molecularly mixed blends with PCBM. The molecularly mixed blends is the result of slow crystallization …

Metal-Organic Frameworks As Potential Platforms For Carbon Dioxide Capture And Chemical Transformation, Wenyang Gao

USF Tampa Graduate Theses and Dissertations

The anthropogenic carbon dioxide (CO₂) emission into the atmosphere, mainly through the combustion of fossil fuels, has resulted in a balance disturbance of the carbon cycle. Overwhelming scientific evidence proves that the escalating level of atmospheric CO₂ is deemed as the main culprit for global warming and climate change. It is thus imperative to develop viable CO₂ capture and sequestration (CCS) technologies to reduce CO₂ emissions, which is also essential to avoid the potential devastating effects in future. The drawbacks of energy-cost, corrosion and inefficiency for amine-based wet-scrubbing systems which are currently used in industry, …

Nanostructured Air Electrodes And Electrochemical Reaction Mechanism Studies For Sodium-Oxygen Batteries, Hossein Yadegari

Electronic Thesis and Dissertation Repository

Alkali metal-O₂ batteries, i.e. Li- and Na-O₂, are considered as the next generation of energy saving technologies with potential application in electric transportation. The high theoretical energy density in these cells is related to the use of high energy alkali metals as negative and oxygen as the positive electrode materials. The performance of alkali metal-O₂ cells is highly dependent on the positive electrode material, where oxygen reduction and evolution reactions take place. Besides, the primary products of oxygen reduction reaction in these cells are typically metal oxides, which are insoluble in nonaqueous electrolytes, resulting in accumulation …

Interaction Between Charge-Transfer States Studied By Magnetic Field Effects, Mingxing Li

Doctoral Dissertations

Organic semiconducting materials, consisting mostly of carbon and hydrogen atoms, provide remarkable promise for electronic applications due to their easy processing, chemical tenability, low costs and environmental-friendly characteristics. For realizing electronic applications such as light emitting diodes and photovoltaic cells, charge-transfer states act as an important intermediate state for recombination and dissociation. Interestingly, magnetic field effects on semiconducting materials have been realized based on the suppression of spin mixing in the charge-transfer states. Although lots of studies have been carried out on investigating the properties of charge-transfer states, little has been done to consider the interaction between them. This thesis …

Development Of A Novel Polymer-Garnet Solid State Composite Electrolyte Incorporating Li-La-Zr-Bi-O And Polyethylene Oxide, Muhammed Ramazan Oduncu

Open Access Theses

Current lithium ion batteries are comprised of organic liquid electrolytes - a mixture of lithium salts and binary solvents such as ethylene carbonate (EC) and dimethyl carbonate (DMC). The main drawbacks of this liquid mixture related to safety are flammability of the organic solvents and chemical instability with the electrode materials. To date, various ceramic and polymer materials have been considered which overcome safety issues. However, a common problem of these solid state materials is that they are not able to provide high ionic conductivity at ambient temperatures. Garnet-type cubic Li7La 3Zr2O12 ceramic material has attracted much interest because of …

Polymerizable Lipids For Controlled Functionalization Of Layered Materials, Kortney Kaye Rupp

Open Access Theses

Self-assembled monolayers (SAM’s) offer a straightforward approach to tailoring the interfacial properties of metals, metal oxides and semiconductors. Noncovalent functionalization of single-layer graphene offers the possibility to finely tune surface chemistry for future applications in electronics. Polymerization of photochemically reactive molecules in a lying-down phase has been used to increase the strength of intermolecular interactions between long alkanes and HOPG substrates. Long-chain fatty acid derivatives with internal diyne groups yield a conjugated ene-yne polymer upon UV irradiation. Diyne lipids with phosphocholine (diyne PC) and phosphoethanolamine (diyne PE) groups offer a charged form of the head group that is robust towards …

Correlation Of Polymer Performance And Hansen Solubility Parameters, Daniel Jobse Mania

Master's Theses

Ready-to-use (RTU) grout is becoming more important to the finish and remodeling construction industry. Market research shows it is a fast-growing product that not only is creating its own space, but is beginning to supplant existing technology.

The original intent of this research was to investigate formulation parameters and how they affect grout performance. It was learned that particle size and oil absorption (OA) value are important filler properties that affect performance as much as adequate packing density and optimal pigment volume concentration (PVC) without going beyond critical PVC (CPVC).

Polymer architecture was also determined to be extremely important, but …

Forcing Cesium Into Higher Oxidation States Via Useful Hard X-Ray Induced Chemistry At Extreme Conditions, Daniel Thomas Sneed

UNLV Theses, Dissertations, Professional Papers, and Capstones

Recent theoretical work published in Nature Chemistry postulates the existence of cesium in high oxidation states when bonding with fluorine. It is thus predicted to behave as a p-block element (such as xenon) at pressures above 5 GPa. At these pressures, fluorine atoms may bond with the inner p-shell electrons forming CsFn, where n may vary from 2 up to 6; thus the oxidation state of Cs may change up to 6+. My research focused on physically synthesizing these compounds and to verify that, given the right conditions, bonding doesn't only occur with valence electrons, but with the inner p-shell …

Metals Additive Manufacturing Powder Aging Characterization, Thomas Russell Lovejoy, Nicholas Karl Muetterties, David Takeo Otsu

Mechanical Engineering

The metallic additive manufacturing process known as selective laser melting requires highly spherical, normally distributed powder with diameters in the range of 10 to 50 microns. Previous observations have shown a degradation in powder quality over time, resulting in unwanted characteristics in the final printed parts. 21-6-9 stainless steel powder was used to fabricate test parts, with leftover powder recycled back into the machine. Powder samples and test specimens were characterized to observe changes across build cycles. Few changes were observed in the physical and mechanical properties of the specimens, however, there were indications of chemical changes across cycles. Potential …

Energy Transfer And Localization In Molecular Crystals, Mitchell A. Wood

Open Access Dissertations

With the aim of developing new technologies for the detection and defeat of energetic materials, this collection of work was focused on using simulations to characterize materials at extremes of temperature, pressure and radiation. Each branch of the work here is collected by which material response is potentially used as the detectable signal.

Where the chemical response is of interest, this work will explore the possibility of non-statistical chemical reactions in condensed-phase energetic materials via reactive molecular dynamics (MD) simulations. We characterize the response of three unique high energy density molecular crystals to different means of energy input: electric fields …

Direct Band Gap Gallium Antimonide Phosphide (Gasbxp1-X) For Solar Fuels., Harry Benjamin Russell

Electronic Theses and Dissertations

Photoelectrochemical water splitting has been identified as a promising route for achieving sustainable energy future. However, semiconductor materials with the appropriate optical, electrical and electrochemical properties have yet to be discovered. In search of an appropriate semiconductor to fill this gap, GaSbP, a semiconductor never tested for PEC performance is proposed here and investigated. Density functional theory (DFT+U) techniques were utilized to predict band gap and band edge energetics for GaSbP alloys with low amount of antimony. The overall objective of this dissertation is to understand the suitability of GaSb_xP_1-x alloys for photoelectrochemical water splitting application. Specifically, …

Synthesis And Performance Analysis Of Polyurethane Foam Nanocomposite For Arsenic Removal From Drinking Water, Faten Bakri Hussein

Theses and Dissertations

Water contamination by various heavy metal pollutants such as, Lead, Arsenic, Cadmium, and Mercury, have severe toxic effects on living organisms and humans. High concentrations of arsenic in drinking water cause serious damage to the central and peripheral nervous systems, as well as, the dermal, cardiovascular, gastrointestinal, and respiratory systems. Arsenic contamination of ground water poses a substantial concern in many countries throughout the world, including the United States.

Considerable research work, aimed at finding and developing various separation and treatment techniques, has been conducted over the past few decades. The conventional treatment methods of arsenic involve coagulation with ferric …

Synthesis Of Acceptors For Use In Donor-Acceptor Copolymers And Characterization Of These Polymers, William D. Walker

Honors Theses

In this thesis, a selenium-derivatized acceptor was synthesized to examine the heavy atom effects of selenium on the position of the frontier molecular orbitals (HOMO/LUMO band gap) as opposed to sulfur in a donor-acceptor copolymer for use in light harvesting and detection applications. Over the course of this research, standard operating protocols for ultraviolet-visible (UV-Vis-NIR) and Fourier transform infrared (FT-IR) spectroscopies, as well as cyclic voltammetry (CV) characterization techniques were established. Once synthesized, the polymers were characterized through use of the established characterization protocols. The selenium-derivatized polymer exhibited a bathochromic shift compared to the sulfur analogue, with a solid-state absorption …

Magnetron Sputtering And Corrosion Of Ti-Al-C And Cr-Al-C Coatings For Zr-Alloy Nuclear Fuel Cladding, Devin Alan Roberts

Masters Theses

The disaster at the Fukushima Daiichi Nuclear Power Plant in March 2011 bought renewed focus to the issue of corrosion in nuclear fuel cladding applications. This thesis reports on the background behind these issues, the investigation strategy, and the analysis of experiments focused on mitigating oxidation of Zr-alloy fuel cladding. This thesis seeks to develop magnetron sputtered Ti-Al-C and Cr-Al-C coatings for Zr-alloy substrates and characterize the as-deposited and corroded samples.

Ti-Al-C and Cr-Al-C coatings were deposited onto ZIRLO, Si, and Al₂O₃ [Aluminum Oxide] substrates under various sputtering conditions. A combinatorial sputtering method was employed to refine …

Doped Tio2 Nanowires For Applications In Dye Sensitized Solar Cells And Sacrifical Hydrogen Production, Qasem Alsharari

Electronic Thesis and Dissertation Repository

This thesis explores the synthesis of metal oxide 1-D nanowires using a sol-gel method in supercritical carbon dioxide (sc-CO₂), as an environmental friendly enabling solvent. Porous nanowires were synthesized and their performance was tested in dye sensitized solar cell and sacrifical hydrogen production. Titanium isopropoxide (TIP) was used as a precursor for titania synthesis while copper, bismuth and indium were examined as dopants, respectively. The sol-gel reactions were catalyzed by acetic acid in CO₂ at a temperature of 60 °C and pressure of 5000 psi. It was observed that acetic acid/monomer ratio > 4 produced nanowires while a …

One-Dimensional Nanostructure And Sensing Applications: Tin Dioxide Nanowires And Carbon Nanotubes, Hoang Anh Tran

Dissertations and Theses

The key challenge for a nanomaterial based sensor is how to synthesize in bulk quantity and fabricate an actual device with insightful understanding of operational mechanisms during performance. I report here effective, controllable methods that exploit the concepts of the "green approach" to synthesize two different one-dimensional nanostructures, including tin oxide nanowires and carbon nanotubes. The syntheses are followed by product characterization and sensing device fabrications as well as sensor performance understanding at the molecular level. Sensor-analyte response and recovery kinetics are also presented.

The first part of the thesis describes bulk-scale synthesis and characterization of tin oxide nanowires by …

Water Condensation And Protein Adsorption On Hybrid Superhydrophobic-Hydrophilic Surfaces, Bikash Mondal

Dissertations, Theses, and Capstone Projects

This thesis describes the study of protein adsorption and water condensation on hybrid superhydrophobic-hydrophilic surfaces for various technological applications such as diagnostics, artificial organs and medical devices, water collection, and heat transfer.

In the chapter 1, a general introduction to wetting theories, superhydrophobic surface, and hybrid surfaces is given. In chapter 2, design and fabrication of a hybrid superhydrophobic surface for studying dropwise condensation and heat transfer is discussed. Effect of surface chemistry and wettability on protein adsorption is discussed in the chapter 3. Finally, in chapter 4, the protein adsorption study on hybrid superhydrophobic surfaces made by 3D-printing and …

New Chemistry For The Growth Of First-Row Transition Metal Films By Atomic Layer Deposition, Joseph Peter Klesko

Wayne State University Dissertations

Thin films containing first-row transition metals are widely used in microelectronic, photovoltaic, catalytic, and surface-coating applications. In particular, metallic films are essential for interconnects and seed, barrier, and capping layers in integrated circuitry. Traditional vapor deposition methods for film growth include PVD, CVD, or the use of plasma. However, these techniques lack the requisite precision for film growth at the nanoscale, and thus, are increasingly inadequate for many current and future applications. By contrast, ALD is the favored approach for depositing films with absolute surface conformality and thickness control on 3D architectures and in high aspect ratio features. However, the …

Dynamic Atomistic Study Of Tunnel Functions In Nanostructured Transitional Metal Oxides, Yifei Yuan

Dissertations, Master's Theses and Master's Reports

Alpha (α-) MnO₂ is a well know transitional metal oxide possessing one dimensional 2×2 (4.6 × 4.6 Ų) tunnels for accommodation of various ions. Such a characteristic tunneled structure has enabled the wide applications of α-MnO₂ in the fields of ion exchange, molecular sieves, biosensor, catalysis and energy storage. This PhD dissertation focuses on the dynamic study of ion transport functionality of α-MnO₂ at atomic level using an aberration corrected scanning transmission electron microscopy equipped with a special holder with a scanning tunneling microscopy probe.

The wide application of in situ TEM studying the dynamic …

Biolabeling Through The Use Of Water-Soluble Colloidal Quantum Dots, Cody Stombaugh

Honors Projects

Nanomaterials continues to be a growing field of study due to their wide range of potential applications. Quantum dots are artificially synthesized crystalline clusters of atoms able to confine electron motion as a result of their incredibly small size. Recently, medical applications of nanomaterials have expanded greatly. Quantum dots are ideal for biolabeling due to their rather narrow photoluminescence emission peaks. By synthesizing quantum dots of a specific diameter, it is possible to predetermine the peak photoluminescence wavelength of a sample. Through ligand exchange and immunoconjugation of the quantum dots with proteins, it is possible to use the quantum dots …

Degradation And Exciton Energy Transfer Studies In Single-Walled Carbon Nanotube Bundles, Abhishek Gottipati

Legacy Theses & Dissertations (2009 - 2024)

Single walled carbon nanotubes (SWNTs) due to their unique optical behavior, large surface area, robust mechanical strength and electrical properties make them one of the ideal candidates for sensing and opto-electronic applications. In this work, we explore the energy transfer (exciton energy transfer-EET) phenomena occurring between nanotubes in bundles, using resonance Raman spectroscopy.

Understanding Electrical Conduction In Lithium Ion Batteries Through Multi-Scale Modeling, Jie Pan

Theses and Dissertations--Chemical and Materials Engineering

Silicon (Si) has been considered as a promising negative electrode material for lithium ion batteries (LIBs) because of its high theoretical capacity, low discharge voltage, and low cost. However, the utilization of Si electrode has been hampered by problems such as slow ionic transport, large stress/strain generation, and unstable solid electrolyte interphase (SEI). These problems severely influence the performance and cycle life of Si electrodes. In general, ionic conduction determines the rate performance of the electrode, while electron leakage through the SEI causes electrolyte decomposition and, thus, causes capacity loss. The goal of this thesis research is to design Si …

Synthesis And Functionalization Of A Triaryldiamine-Base Photoconductive/Photorefractive Composite, And Its Application To Aberrated Image Restoration, Yichen Liang

Doctoral Dissertations

"Organic photorefractive (PR) composites have recently emerged as an important class of materials for applications including high-density data storage, optical communication, and biomedical imaging. In an effort to further improve their performance, this study focused on the utilization of functionalized semiconductor nanocrystals to photosensitize triaryamine (TPD)-based PR composites, as well as the application of TPD-based PR composites in the restoration of aberrated optical information. A novel approach to functionalize CdSe quantum dot (QCdSe) was firstly introduced where the sulfonated triarydiamine (STPD) was used as charge-transporting ligand to passivate QCdSe. TPD-based photoconductive and PR composites were photosensitized with the STPD-passivated QCdSe …

Improving The Engineering Properties Of Pla For 3d Printing And Beyond, Carmen R. Rocha

Open Access Theses & Dissertations

Additive manufacturing (AM), now more commonly known as 3D printing, has been classified as efficient, fast, and practical in the prototyping sector of product development. In the work presented here, we will use one of the AM techniques known as Material extrusion 3D printing (ME3DP), which has all the advantages of AM. However, one of the biggest challenges facing ME3DP technologies is the limitation of the range of materials used by this technique. Acrylonitrile butadiene styrene (ABS) and poly-lactic acid (PLA) are currently the most common thermoplastics materials used in ME3DP because of their ability to melt and be reprocessed. …

Optimizing Solvent Blends For A Quinary System, Thomas L. Hoy

Williams Honors College, Honors Research Projects

The Department of Polymer Engineering had received a grant from the Keck foundation to produce a process in which hundreds of copolymers can be formulated, synthesized, analyzed and then extrapolated to produce the optimal polymer for the desired material property. This process involves synthesizing approximately fifty polymers in a custom apparatus, none of which necessarily have the same monomer components. This leads to issue of which solvent or blend of solvents to use that would sufficiently dissolve both monomers and the resulting copolymer. If the monomers are not completely dissolved, a homogenous reaction will be impossible and if the copolymer …

Drying Methods For The Fabrication Of Polymer Foam Material, Dalton Echard

Theses and Dissertations

This is a report on the study of the drying of nanoporous polymer foam material fabricated by photolithogtaphic methods. Three drying methods were employed, which were air drying, supercritical drying and freeze drying. After fabrication and drying, physical properties of the polymer foams were measured. These measurements included density of the material, Young’s modulus, surface area, and the shape of the skeletal particles. The measurements determined the effect of the polymer concentration and the effect of drying methods. It was determined that polymer concentration had a much larger effect on the properties of the materials than the drying method.