Engineering Commons^™

Relating Detonation Parameters To The Detonation Synthesis Of Nanomaterials, Martin Langenderfer

Doctoral Dissertations

“This research investigates the physical and chemical processes that contribute to the detonation synthesis of silicon carbide nanoparticles. Bulk production of SiC nanoparticles through detonation is possible due to pressures achieved over 20 GPa and temperatures over 2000 K as well as quenching rates in excess of 13 billion K/second. These conditions catalyze reaction and bottom-up molecular growth while retaining particles < 100 nm in diameter. In this work, detonation synthesis of SiC was demonstrated by incorporation of polycarbosilane, an SiC precursor material, into an RDX/TNT explosive matrix prior to detonation. Detonation Synthesis of SiC was also accomplished by reacting elemental silicon with carbon liberated by the detonation of negatively oxygen balanced TNT. Hydrodynamic simulation of a 60:40 mass ratio RDX/TNT detonation created conditions thermodynamically suitable to produce cubic silicon carbide within the first 500 nanoseconds after the passage of the detonation wave while carbon remains chemically reactive for molecular formation. Simulations and experimental tests indicated that loading configuration and impedance mismatch of the precursor additives used in detonation synthesis results in conditions in the additives that exceed the accepted detonation pressure of the explosive by greater than three times. Finally, a full factorial experimental design showed increasing silicon concentration, reducing silicon size, and reducing oxygen balance by adjusting the ratio of RDX to TNT decreased the explosives detonation pressure by 20% and increased the soot yield and concentration of SiC observed in the detonation products by 82% and 442% respectively”--Abstract, page iv.

Designing Transition Metal Chalcogenides Electrocatalyst Surfaces For High-Efficiency Water Oxidation, Umanga De Silva

Doctoral Dissertations

”The rising demand for energy security and reducing fossil fuel dependence has prompted researchers to search for a clean, sustainable, and efficient energy generation system with low environmental impact. Water electrolysis has been identified as one of the most important processes satisfying the above needs to generate hydrogen as a clean fuel. Two half-cell reactions of oxygen evolution reaction (OER) at the anode and hydrogen evolution reaction (HER) at the cathode comprise the main process of water electrolysis. However, the oxygen evolution reaction is the most crucial step for efficient water splitting. Traditionally, metal oxides have been utilized as catalysts …

Continuous-Flow Synthesis Of Fine Chemicals And Pharmaceutical Compounds Over Intelligent Organocatalysts With Bifunctional Reactivity, Abdo-Alslam Alwakwak

Doctoral Dissertations

“Many biological systems that utilize organic active sites to catalyze reactions under mild conditions invoke cooperative catalytic pathways, whereby two or more active sites work together to activate the reactant(s). The use of cooperative (bifunctional) catalysts and continuous flow chemistry (a reaction within the narrow channels of a micro‐ or microfluidic reactor) are commonplace in sustainable chemical transformation and attract a great deal of interest with respect to economic and environmentally-sustainable production of fine chemicals, pharmaceuticals, and agrochemicals, water treatment, as well as upgrading of biomass feedstocks. Although, some methods have been developed for immobilization of bifunctional catalysts for cooperative …

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 …

Mass Spectrometry Analysis Of Contaminants Of Emerging Concern: Nanoparticles, Algal Toxins, And Cyanotoxins In Natural Waters And Their Potential Health Impacts, Ariel R. Donovan

Doctoral Dissertations

“The analysis of contaminants of emerging concern is critical to protecting environmental health. In the presented dissertation, two groups of contaminants of emerging concern were assessed using mass spectrometry methods: nanoparticles and algal and cyanotoxins.

Analysis of metal oxide nanoparticles in environmental matrices has been a challenging issue, as most traditional methods require complicated sample preparation methods or that can alter or destroy the nanoparticles in the system. Single particle inductively coupled plasma mass spectrometry (SP-ICP-MS) methods were used to detect metal oxide nanoparticles in surface waters and their removal through drinking water treatment simulations while retaining all information regarding …

Development Of Functional Ionic Liquids For Separation And Recovery Of Rare Earth Elements, Mostafa Khodakarami

Doctoral Dissertations

“This research focused on the design and synthesis of task-specific ionic liquids for enhanced extraction and separation of rare earth elements (REEs). Two novel ammonium-based functional ionic liquids (FILs) with oxygen donating groups: trioctyl(2-ethoxy-2-oxoethyl)ammonium dihexyl diglycolamate, [OcGBOEt][DHDGA], and tricaprylmethylammonium dihexyl diglycolamate, [A336][DHDGA] were synthesized and tested for the recovery and separation of selected REEs from aqueous solutions. Functionalities with different denticities were incorporated into both anionic and cationic parts of ionic liquids, which are solely composed of incinerable atoms including C, H, O, and N. The structural, physical, and chemical properties of the synthesized FILs were studied using nuclear magnetic …

Polyurea Aerogels: From Nanoscopic To Macroscopic Properties, Tahereh Taghvaee

Doctoral Dissertations

"The morphology of a material is intrinsically a qualitative property and in order to relate nanomorphology to synthetic conditions, it is necessary to express nano/micro-structure quantitatively. In this context, polyurea aerogels were chosen as a model system with demonstrated potential for rich nanomorphology and being guided by a statistical Design-of-Experiments model, a large array of materials (208) with identical chemical composition, but quite different nanostructures were prepared. By reflecting upon the SEM images, it was realized that our first pre-verbal impression about a nanostructure is related to its openness and texture; the former is quantified by porosity (Π), and the …

Synthesis And Applications Of Ceramic (Silicon Carbide And Silicon Nitride), Metallic (Cobalt(0)) And Polymeric (Polyurethane) Aerogels, Parwani M. Rewatkar

Doctoral Dissertations

"A new method has been demonstrated for the synthesis of monolithic ceramic and purely metallic aerogels from xerogel powder compacts, and the use of polyurethane aerogels based on cyclodextrins as efficient desiccants.

I. Highly porous ( > 80%) monolithic SiC and Si₃N₄, aerogels were prepared from compressed compacts of polyurea-crosslinked silica xerogel powders. The process is time efficient as solvent-exchange through powders is fast, and energy efficient as it bypasses drying with supercritical fluids. The final ceramic objects were chemically pure, sturdy, with compressive moduli at 37 ±7 MPa and 59 ± 7 MPa, and thermal conductivities …

Electrodeposition Of Epitaxial Metal Thin Films On Silicon For Energy Conversion And Flexible Electronics, Qingzhi Chen

Doctoral Dissertations

"This research focuses on epitaxial electrodeposition of two coinage metals: Au and Ag thin films on the silicon surface and their applications in flexible electronics and energy conversion and storage. The first paper: Photoelectrochemistry of ultrathin, semi-transparent, and catalytic gold films electrodeposited epitaxially onto n-silicon (111) describes the epitaxial electrodeposition of Au thin films on n-type Si using a simple HAuCl4 bath and the photoelectrochemical properties of the Au-Si junction barrier. The effect of the Au layer on the interfacial energetics as well as the stability of the photoelectrode as a function of the Au coverage/thickness is determined in a …

Nanomorphology Dependent Optical And Mechanical Properties Of Aerogels, Chandana Mandal

Doctoral Dissertations

"Aerogels are very low density, light weight open pore materials. A hypothesis that is under intense current investigation by the scientific community states that the mechanical properties of nanostructured polymers depend on their nanomorphology. Aerogels are nanostructured ultra-lightweight nanoporous materials with skeletal frameworks that can display a wide range of nanomorphologies. Thereby aerogels comprise a suitable platform for testing not only that hypothesis but also a wide range of other properties such as light scattering for applications, for example, in thermally insulating windows.

To study the mechanical properties of nanostructured matter as a function of nanomorphology, various shape-memory polyurethane aerogels …

Three-Dimensional Nanotube Arrays For Solar Energy Harvesting And Production Of Solar Fuels, Wipula P. R. Liyanage

Doctoral Dissertations

"Over the past decade extensive research has been carried out on photovoltaic semiconductors to provide a solution towards a renewable energy future. Fabricating high-efficiency photovoltaic devices largely rely on nanostructuring the photoabsorber layers due to the ability of improving photoabsorption, photocurrent generation and transport in nanometer scale. Vertically aligned, highly uniform nanorods and nanowire arrays for solar energy conversion have been explored as potential candidates for solar energy conversion and solar-fuel generation owing to their enhanced photoconversion efficiencies.

However, controlled fabrication of nanorod and especially nanotube arrays with uniform size and shape and a pre-determined distribution density is still a …

Electrodeposited Semiconductor Nanostructures & Epitaxial Thin Films For Flexible Electronics, Naveen Kumar Mahenderkar

Doctoral Dissertations

"Single-crystal Si is the bedrock of semiconductor devices due to the high crystalline perfection which minimizes electron-hole recombination, and the dense native silicon oxide which minimizes surface states. To expand the palette of electronic materials beyond planar Si, an inexpensive source of highly ordered material is needed that can serve as an inert substrate for the epitaxial growth of grain boundary-free semiconductors, photonic materials, and superconductors. There is also a need for a simple, inexpensive, and scalable fabrication technique for the growth of semiconductor nanostructures and thin films. This dissertation focuses on the fabrication of semiconducting nanowires (polycrystalline Ge & …

Electrodeposited Epitaxial Cobalt Oxides And Copper Metal, Caleb M. Hull

Doctoral Dissertations

"Electrochemical deposition methods are presented for the deposition of Co(OH)₂ and Cu metal. Paper I shows the deposition of β-Co(OH)₂ on Ti through electrochemical reduction of [Co(en)₃]³⁺ to [Co(en)₃]²⁺ in 2M NaOH. The catalytic properties of the deposited Co(OH)₂ towards water oxidation is found comparable to Co₃O₄, with the surface of the Co(OH)₂ converting to CoOOH during the reaction. Paper II gives the conditions suitable for epitaxial growth of Co(OH)₂ on Au(100), Au(110), and Au(111) following the same reduction mechanism as described in Paper I. …

Single Particle-Inductively Coupled Plasma-Mass Spectrometry Technology Development For Metallic Nanoparticle Characterization In Complex Matrices, Yongbo Dan

Doctoral Dissertations

"As the rapid growing of nanotechnology, the release of engineered nanoparticles (ENPs) into the environment is inevitable. After entering the real environment, ENPs tend to react with different components of the ecosystem (e.g. water, soil, air, plants) and make their characterization difficult. Analyzing ENPs in these complex matrices still remains as a grand challenge. ENPs characterization is normally the first step of risk assessment. Current analytical techniques have shown some limitations in revealing the unique characteristics of ENPs in complex matrices and reliable analytical techniques are in urgent need. Single particle inductively coupled plasma mass spectrometry (SP-ICP-MS) is an emerging …

Bioactivity/Cytotoxicity Of Micro-/Nano-Materials And Novel Development Of Fiber-Optic Probes For Single Cell Monitoring, Qingbo Yang

Doctoral Dissertations

"Manufactured nano-/micro-materials (MNMs) have been widely used and their interactions with niche biological environment are highly concerned for both of their biohazardous and bioactive effects, whereas no available comprehensive evaluations or regulations have been provided yet. This dissertation thus focuses on three major aspects: 1) fundamental toxicity understandings of a typical MNMs (zinc oxide nanoparticles), 2) bioactivity evaluations of representative bioactive MNMs, and 3) development of novel micro-probes for high spatial resolution monitoring. Firstly, the NP's concentration, irradiation, hydrodynamic size, and the localized pH, ionic strength, NP zeta-potential as well as dissolved oxygen levels were found correlated with the production …

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 …

The Synthesis And Characterization Of Water-Reducible Nanoscale Colloidal Unimolecular Polymer (Cup) Particles, Cynthia J. Riddles

Doctoral Dissertations

"The coatings industry has adapted to more stringent guidelines in paint formulations. Current VOC (volatile organic compound) limits placed by the federal government have pushed the industry toward the development of paint formulations which have very little to no VOC's. The development of Colloidal Unimolecular Polymer (CUP) particles is a step in the direction of providing a resin system which exists in zero VOC aqueous dispersion.

The CUP particles are a part of the polymer field of Single Chain Nano Particles (SCNP) and ranged in diameters of 3-9 nm. The research presented in this dissertation describes the synthesis and design …

Mechanical Characteristics Of Organically Modified Fly Ash-Kaolinite Mixtures, Xin Kang

Doctoral Dissertations

"Fly ash is a hazardous waste material to the environment. Beneficial reuse of fly ash, however, brings economic and environmental benefits, i.e., decreases the cost of disposal, reduces greenhouse gas emission, and improves mechanical properties of construction materials. Due to the lack of pozzolanic properties, the reuse rate of Class F fly ash in geotechnical engineering is relatively low (ACAA 2013). In order to promote the effectiveness and sustainability of high volume reuse of class F fly ash in geotechnical engineering, biopolymers (Chitosan, and Xanthan gum) and synthetic polymers (Polyethylene Oxide, PEO) were used instead of the traditional stabilizers to …

Pyrochemical Changes In Missouri Halloysite, Frank Joseph Zvanut

Doctoral Dissertations

"For centuries it has been known that the application of heat to a clay or a clay body produces changes that make it an entirely different substance from the original raw clay. Ever since the earliest civilizations produced crude building brick by baking formed clay bodies in the sun's rays, mankind has been speculating on the nature of the changes that convert soft, friable, plastic clays into hard, strong, non-plastic, rock-like masses. It has been only within the last two decades, however, that progress has been made in the solution of problems dealing with the resultant products in fired clay …