Physical Sciences and Mathematics Commons^™

Pisa Printing Microneedles With Controllable Aqueous Dissolution Kinetics, Aaron Priester, Jimmy Yeng, Yuwei Zhang, Krista Hilmas, Risheng Wang, Anthony J. Convertine

Chemistry Faculty Research & Creative Works

This study focused on the development of high-resolution polymeric structures using polymer-induced self-assembly (PISA) printing with commercially available digital light-processing (DLP) printers. Significantly, soluble solids could be 3D-printed using this methodology with controllable aqueous dissolution rates. This was achieved using a highly branched macrochain transfer agent (macro-CTA) containing multiple covalently attached CTA groups. In this work, the use of acrylamide as the self-assembling monomer in isopropyl alcohol was explored with the addition of N-(butoxymethyl)acrylamide to modulate the aqueous dissolution kinetics. PISA-printed microneedles were observed to have feature sizes as small as 27 μm, which was close to the resolution limit …

Synthesis, Densification, And Cation Inversion In High Entropy (Co,Cu,Mg,Ni,Zn)Al2o4 Spinel, Cole A. Corlett, Nina Obradovic, Jeremy Lee Watts, Eric W. Bohannan, William Fahrenholtz

Materials Science and Engineering Faculty Research & Creative Works

The synthesis, densification behavior, and crystallographic site occupancy were investigated for four different spinel-based ceramics, including a high-entropy spinel (Co_0.2Cu_0.2Mg_0.2Ni_0.2 Zn_0.2)Al₂O₄. Each composition was reacted to form a single phase, but analysis of X-ray diffraction patterns revealed differences in cation site occupancy with the high-entropy spinel being nearly fully normal. Densification behavior was investigated and showed that fully dense ceramics could be produced by hot pressing at temperatures as low as 1375°C for all compositions. Vickers' hardness values were at least 10 GPa for all compositions. The …

Relating Detonation Parameters To The Detonation Synthesis Of Silicon Carbide, Martin Langenderfer, Eric W. Bohannan, Jeremy Lee Watts, William Fahrenholtz, Catherine E. Johnson

Chemistry Faculty Research & Creative Works

Detonation synthesis of silicon carbide (SiC) nanoparticles from carbon liberated by negatively oxygen balanced explosives was evaluated in a 23 factorial design to determine the effects of three categorical experimental factors: (1) cyclotrimethylene-trinitramine (RDX)/2,4,6-trinitrotoluene (TNT) ratio, (2) silicon (Si) additive concentration, and (3) Si particle size. These factors were evaluated at low and high levels as they relate to the detonation performance of the explosive and the solid Si-containing phases produced. Detonation velocity and Chapman-Jouguet (C-J) detonation pressure, which were measured using rate stick plate dent tests, were evaluated. Solid detonation product mass, silicon carbide product concentration, and residual silicon …

Theranostic Copolymers Neutralize Reactive Oxygen Species And Lipid Peroxidation Products For The Combined Treatment Of Traumatic Brain Injury, Aaron Priester, Richard Waters, Ashleigh Abbott, Krista Hilmas, Klaus Woelk, Hunter A. Miller, Aria W. Tarudji, Connor C. Gee, Brandon Mcdonald, Forrest M. Kievit, Anthony J. Convertine

Chemistry Faculty Research & Creative Works

Traumatic brain injury (TBI) results in the generation of reactive oxygen species (ROS) and lipid peroxidation product (LPOx), including acrolein and 4-hydroxynonenal (4HNE). The presence of these biochemical derangements results in neurodegeneration during the secondary phase of the injury. The ability to rapidly neutralize multiple species could significantly improve outcomes for TBI patients. However, the difficulty in creating therapies that target multiple biochemical derangements simultaneously has greatly limited therapeutic efficacy. Therefore, our goal was to design a material that could rapidly bind and neutralize both ROS and LPOx following TBI. To do this, a series of thiol-functionalized biocompatible copolymers based …

Effects Of Vacancies And Electron Temperature On The Electron Phonon Coupling In Cubic Silicon Carbide And Their Connection To The Inelastic Thermal Spike, Salah Al-Smairat

Doctoral Dissertations

“The electron-phonon interaction is an important interaction in many solids as it influences transport phenomena and related quantities such as the electrical and thermal conductivities, especially in nuclear and space applications. The importance of the electron-phonon interaction in primary damage production in 3C-SiC is the subject of this research.

The electron-phonon coupling factor was calculated using a hybrid Density Functional Perturbation Theory - Classical Electron Gas model. The coupling factor was calculated as a function of electron temperature in pristine and defective 3C-SiC, and relaxed defective cells. The electron-phonon coupling is found to depend strongly on the electronic temperature and …

Findings Report: Virtual Workshop On ‘Resilient Supply Of Critical Minerals’, Marek Locmelis, Angela D. Lueking, Michael S. Moats, Kwame Awuah-Offei, Lana Z. Alagha, Mark W. Fitch, Alanna Krolikowski, Shelby Clark

Geosciences and Geological and Petroleum Engineering Faculty Research & Creative Works

Executive Summary
On August 2-3, 2021, the Thomas J. O’Keefe Institute for Sustainable Supply of Strategic Minerals at Missouri University of Science and Technology (Missouri S&T) hosted the NSF-funded virtual workshop ‘Resilient Supply of Critical Minerals’. The workshop was convened via Zoom and attracted 158 registrants, including 108 registrants from academia (61 students), 30 registrants from government agencies, and 20 registrants from the private sector. Four topical sessions were covered:

A. Mineral Exploration and Source Diversification.
B. Supply Chain and Policy Issues.
C. Improving Mineral Recycling and Reprocessing Technologies.
D. Technological Alternatives to Critical Minerals.

Each topical session was composed …

Semi-Empirical Modeling Of Liquid Carbon's Containerless Solidification, Philip C. Chrostoski

Doctoral Dissertations

“Elemental carbon has important structural diversity, ranging from nanotubes through graphite to diamond. Previous studies of micron-size core/rim carbon spheres extracted from primitive meteorites suggest they formed around such stars via the solidification of condensed carbon-vapor droplets, followed by gas-to-solid carbon coating to form the graphite rims. Similar core/rim particles result from the slow cooling of carbon vapor in the lab. The long-range carbon bond-order potential was used to computationally study liquid-like carbon in (1.8 g/cm³) periodic boundary (tiled-cube supercell) and containerless (isolated cluster) settings. Relaxations via conjugate-gradient and simulated-annealing nucleation and growth simulations using molecular dynamics were …

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.

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 …

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 …

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 …

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 …

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 …

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 …

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 …

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 …

Removal Of Antimony And Bismuth From Copper Electrorefining Electrolyte By Two Proprietary Solvent Extraction Extractants, Andrew Artzer

Masters Theses

"Antimony and bismuth are two of the most problematic impurities in copper electrorefining (ER). Because of this, much research has been done investigating the ways to remove them. Processes that are currently being used industrially include anode additions, liberators, ion exchange (IX), and solvent extraction (SX). Of these, liberators and anode additions are the most common while SX is the least, mostly being used for arsenic removal. There are other methods that have been evaluated, but are not in commercial use. These include the use of various electrolyte additives, and adsorbents such as bentonite clay and heavy metal sulfates.

Two …

Detonation Synthesis Of Alpha-Variant Silicon Carbide, Martin Langenderfer, Catherine E. Johnson, William Fahrenholtz, Vadym Mochalin

Mining Engineering Faculty Research & Creative Works

A recent research study has been undertaken to develop facilities for conducting detonation synthesis of nanomaterials. This process involves a familiar technique that has been utilized for the industrial synthesis of nanodiamonds. Developments through this study have allowed for experimentation with the concept of modifying explosive compositions to induce synthesis of new nanomaterials. Initial experimentation has been conducted with the end goal being synthesis of alpha variant silicon carbide (α-SiC) in the nano-scale. The α-SiC that can be produced through detonation synthesis methods is critical to the ceramics industry because of a number of unique properties of the material. Conventional …

Mitigation Of Environmental Hazards Of Sulfide Mineral Flotation With An Insight Into Froth Stability And Flotation Performance, Muhammad Badar Hayat

Doctoral Dissertations

"Today's major challenges facing the flotation of sulfide minerals involve constant variability in the ore composition; environmental concerns; water scarcity and inefficient plant performance. The present work addresses these challenges faced by the flotation process of complex sulfide ore of Mississippi Valley type with an insight into the froth stability and the flotation performance. The first project in this study was aimed at finding the optimum conditions for the bulk flotation of galena (PbS) and chalcopyrite (CuFeS₂) through Response Surface Methodology (RSM). In the second project, an attempt was made to replace toxic sodium cyanide (NaCN) with the biodegradable chitosan …

Modulated Photothermal Radiometry: Detector Sensitivity Study And Experimental Setup, Jessica Nicole Seals

Masters Theses

"This thesis outlines the development of a system used for determining the surface thermal diffusivity of both non-irradiated and irradiated materials. The motivation for this work is to establish a modulated photothermal radiometry (PTR) system on the campus of Missouri University of Science and Technology. One of the main efforts described in this thesis is the design and construction of the physical apparatus. Along the way, it was necessary to perform a detailed sensitivity analysis of the system to determine whether the expected signal emitted from the sample falls within the bounds of detectivity for the HgCdTe (MCT) detector used …

Research And Development Of Optically Transparent Join With Low Processing Temperatures, Eric Kevin Muskovin

Masters Theses

The purpose of this study was to investigate durable solar cell cover glass joins produced by diffusion bonding with deep eutectic solvents (DES) and to develop a novel process of joining optically transparent materials at low temperatures. A joined PV cell-glass specimen was characterized using Raman, μ-FTIR, SEM-EDS, and thin-film XRD. DESs were created with malonic acid (MAL) and choline chloride (ChCl) of varying composition factors (CF; CF=MAL/ChCl). Joining borosilicate glass coupons was attempted using DESs with CF = 0.65 and 1 at temperatures between 100-150 °C for 20 hours. Joining the glass coupons failed at all temperatures and oxygen …

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 & …

Functionalized Nanoporous Carbon Scaffolds For Hydrogen Storage Applications, Christopher L. Carr

Doctoral Dissertations

"Recent efforts have demonstrated confinement in porous scaffolds at the nanoscale can alter the hydrogen sorption properties of metal hydrides, though not to an extent feasible for use in onboard hydrogen storage applications, proposing the need for a method allowing further modifications. The work presented here explores how the functionalization of nanoporous carbon scaffold surfaces with heteroatoms can modify the hydrogen sorption properties of confined metal hydrides in relation to non-functionalized scaffolds (FS). Investigations of nanoconfined LiBH₄ and NaAlH₄ indicate functionalizing the carbon scaffold surface with nitrogen can shift the activation energy of hydrogen desorption in excess of …

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. …

Homogenization Of Plastic Deformation In Heterogeneous Lamella Structures, Rui Yuan, Irene J. Beyerlein, Caizhi Zhou

Materials Science and Engineering Faculty Research & Creative Works

It has been shown that unlike its constituent nanocrystalline (NC) phase, a heterogeneous lamella (HL) composite comprising NC and coarse-grain layers exhibits greatly improved ductility. To understand the origin of this enhancement, we present a 3D discrete dislocation, crystal plasticity finite element model to study the development of strains across this microstructure. Here we show that the HL structure homogenizes the plastic strains in the NC layer, weakening the effect of strain concentrations. These findings can provide valuable insight into the effects of material length scales on material instabilities, which is needed to design heterogeneous structures with superior properties.

Overview Of Co₂ Leakage Problems And Sealants For Co₂ Leakage Remediation, Shudai Peng

Masters Theses

"Excessive Carbon Dioxide (CO₂) emission has become a serious issue and caused lots of environmental problems. Carbon Capture and Storage (CCS) program has been developed to reduce the CO₂ content in the atmosphere. CO₂ storage has been targeted mainly on depleted oil or gas reservoirs and deep saline aquifers. However, leakage could occur through wellbores, cap rocks, formation faults, and fractures during and after CO₂ injection. To minimize the risk, different types of sealants have been investigated to prevent CO₂ leaks. The aim of this thesis is to provide a comprehensive review of the materials which could be used as …

Dirac Surface States Of Magnetic Topological Insulators, Seng Huat Lee

Doctoral Dissertations

"Magnetic topological insulator (TI) has been theoretically proposed to be a platform for inducing magnetic monopole and exhibit fascinating quantum phenomena, whereas topological superconductor can host Majorana fermions, particles that are their own antiparticles, which can be manipulated for topological quantum computing. In this dissertation, we experimentally demonstrated that by intercalation of different transition metals in the van der Waals gaps of Bi₂Se₃ TI, magnetism and even superconductivity can be induced. In Fe_xBi₂Se₃, antiferromagnetism is induced with a transition temperature at ~ 100 K. Coexistence of the Dirac surface state with …

Computational Fluid Dynamics Study Of Molten Steel Flow Patterns And Particle-Wall Interactions Inside A Slide-Gate Nozzle By A Hybrid Turbulent Model, Mahdi Mohammadi-Ghaleni, Mohsen Asle Zaeem, Jeffrey D. Smith, Ronald J. O'Malley

Materials Science and Engineering Faculty Research & Creative Works

Melt flow patterns and turbulence inside a slide-gate throttled submerged entry nozzle (SEN) were studied using Detached–Eddy Simulation (DES) model, which is a combination of Reynolds–Averaged Navier–Stokes (RANS) and Large–Eddy Simulation (LES) models. The DES switching criterion between RANS and LES was investigated to closely reproduce the flow structures of low and high turbulence regions similar to RANS and LES simulations, respectively. The melt flow patterns inside the nozzle were determined by k–ε (a RANS model), LES, and DES turbulent models, and convergence studies were performed to ensure reliability of the results. Results showed that the DES model has significant …

The Anisotropy Of Hexagonal Close-Packed And Liquid Interface Free Energy Using Molecular Dynamics Simulations Based On Modified Embedded-Atom Method, Ebrahim Asadi, Mohsen Asle Zaeem

Materials Science and Engineering Faculty Research & Creative Works

This work aims to comprehensively study the anisotropy of the hexagonal close-packed (HCP)-liquid interface free energy using molecular dynamics (MD) simulations based on the modified-embedded atom method (MEAM). As a case study, all the simulations are performed for Magnesium (Mg). The solid-liquid coexisting approach is used to accurately calculate the melting point and melting properties. Then, the capillary fluctuation method (CFM) is used to determine the HCP-liquid interface free energy (γ) and anisotropy parameters. In CFM, a continuous order parameter is employed to accurately locate the HCP-liquid interface location, and the HCP symmetry-adapted spherical harmonics are used to expand γ …