Engineering Commons^™

Reconfiguration-Driven Assembly Of Inorganic Nanomembranes, Divya Jyoti Prakash

Chemical and Biological Engineering ETDs

This thesis focuses on the guided self-assembly of metastable nanomembranes (NMs) that are either amorphous or polycrystalline. Guided self-assembly of NMs is a robust and scalable method to obtain a variety of three-dimensional structures such as helices, rolled-up tubes, and networks of interconnected channels. These 3D structures have important applications as on-chip actuators, sensors, inductors, transformers, waveguides, and antennas. Furthermore, a large amount of strain and strain gradient can be imparted in NMs by bending them to a nanoscale and microscale radius of curvature, making guided self-assembly on NMs a viable route to extreme strain engineering of amorphous and polycrystalline …

Gold Thin Film Electrodes For High Sensitivity & Selectivity Electrochemical Detection Of Arsenite In Water, Tybur Q. Casuse Driovínto

Civil Engineering ETDs

This is partial fulfillment of a dissertation defense on electrochemical detection of Arsenic (As) in water using gold (Au) nanofilms as sensing electrodes. The maximum contaminant level of Arsenic in drinking water is set at 10 g L^-1 by the WHO and USEPA. Electrochemical detection by linear stripping voltammetry has comparable detection limits to more expensive laboratory-based methods but with added benefits of being portable and manufacturable. The work has developed sputtered and crystallographically oriented nanofilms for detection of trace As (III). Ultraflat Au(111) oriented thin films, Au(UTF), were compared to single crystal model electrodes to identify the impacts …

Antimicrobial Activity And Mechanism Of Amyloid Proteins And Synthetic Conjugated Polyelectrolytes, Fahimeh Maghsoodi

Nanoscience and Microsystems ETDs

Although the exact cause of Alzheimer’s disease (AD) is still unknown, it is widely considered that the accumulation of amyloid plaques composed of the amyloid-β (Aβ) peptide in the brain is linked to neurodegeneration. Co-localization of viral DNA with Aβ plaques, the association of brain infection and AD, and research indicating the protective effect of Aβ against bacteria and fungi in mice and human cells have led to the hypothesis that Aβ expression and deposition may be central to its function as an antimicrobial peptide (AMP). In my thesis research, we seek to elucidate how Aβ functions as an AMP …

Modeling And Performance Analysis Of Deb Based Hydrogen Getters, John A. Matteson

Chemical and Biological Engineering ETDs

Hydrogen getter materials are used to irreversibly absorb hydrogen gas in sealed environments. The DEB based getter system, despite finding widespread use in this application, still posses challenges with respect to experimental performance analysis and fundamental understanding of reaction mechanism. The second chapter of this report addresses the experimental challenges of this getter system by demonstrating the utility and experimental strengths of a custom magnetic suspension balance (MSB) based gravimetric sorption system. This apparatus enables performance evaluation in process relevant conditions including dilute mixed gas environments which our results indicate is necessary for accurate performance evaluation of getter systems. Chapter …

Controlling The Emission Of Volatile Platinum Oxides To The Vapor Phase In Diesel Oxidation Catalysts, Arnab Ghosh

Nanoscience and Microsystems ETDs

Pt-based catalysts are used for the treatment of emissions from vehicles, particularly in Diesel oxidation catalysts (DOCs). Three-way catalysts are treated at temperatures ranging from 950℃-1050℃ while DOCs are aged at 800℃ for 50 hrs. At 800°C, Pt reacts with O₂ to form PtO₂ which has a high vapor pressure and can be transported through the vapor phase. These accelerated aging conditions lead to the formation of large Pt particles causing a loss of catalytic activity. In this thesis, we used model thin-film catalysts that made it possible to quantify the emission of Pt to the vapor phase …

Prediction Of Self-Diffusion Constants In Model And Real Systems Using Machine Learning, Joshua P. Allers

Chemical and Biological Engineering ETDs

Understanding diffusion of chemical compounds is important for the design and optimization of many chemical engineering and energy processes. Recent modifications to the Darken equation allow for accurate prediction of Maxwell-Stefan (MS) diffusion in mixtures. Still, there are few practical applications due to the requirement of individual self-diffusion constants. A reliable predictive model for self-diffusion constants would be highly valuable when used in conjunction with the modified Darken equation. Here, we show that Machine Learning (ML) can be used to develop generalized models for self-diffusion in Lennard Jones (LJ) systems and real systems of pure solutions. The use of Artificial …

Copper Electrodeposition In Full Wafer Thickness Through-Silicon Vias, Rebecca P. Schmitt

Chemical and Biological Engineering ETDs

Through-silicon vias (TSVs) are a key interconnect technology for advanced packaging of microelectronic devices, and full wafer thickness TSVs are required for certain microelectromechanical systems (MEMS) applications. In this work, electrolytes containing copper sulfate, an acid, chloride, and Tetronic 701 suppressor were implemented for Cu filling of high aspect ratio (10:1), full wafer thickness TSVs. For each electrolyte system, rotating disk electrode voltammetry was used to identify a voltage range for bottom-up Cu filling in the TSVs. Die level feature filling was performed using voltage ramping, which moved active deposition through the vias to yield void-free Cu features. During voltage-controlled …

Understanding The Role Of Atom Trapping In The Evolution Of Hydrocarbon Transformation Catalyst Morphology, Griffin Canning

Chemistry and Chemical Biology ETDs

Converting alkanes to other, more chemically and economically valuable molecules requires catalysts that can survive elevated temperatures and highly reducing environments. These environments can cause many metal-nanoparticle based catalysts to sinter rapidly, causing a loss of activity. They must also tolerate the coke formation, as well, since coke can restrict access to active sites by gas phase molecules, thus lowering catalytic activity. While there are routes to improve both the sinter and coke resistance of catalysts, an alternative strategy is to develop a protocol for regenerating the activity of the catalyst in question when coke formation or sintering becomes problematic. …

Atom Trapping And Its Role On The Nucleation & Growth Of Platinum Nanoparticles, Deepak Kunwar

Chemistry and Chemical Biology ETDs

Diesel oxidation catalysts deactivate due to Pt sintering, a major problem in automotive industries. To make sure they operate effectively throughout the lifetime of the vehicle, automotive industries are putting an excessive amount of Pt. There is a need to develop a catalyst that serves long term performance with minimal use of Pt. Jones et al^.1 demonstrated that ceria traps Pt atoms. His work generated some logical and valid questions such as what is the mechanism for the formation of anomalously large Pt particles? What is the upper limit of Pt metal loading in the form of single atoms …

Synthesis, Self-Assembly And High-Pressure Properties Of Nanoparticles And Hybrid Nanocomposites, Lingyao Meng

Nanoscience and Microsystems ETDs

Nanoparticles have gained significant scientific interests owing to their unique structural dimensions, size- and shape-tunable properties, and numerous fascinating applications, from opto-electronics, sensor devices, to energy, environmental, and medical fields. Furthermore, the synergistic integration of other materials, including organic polymers, with nanoparticles provides new opportunities and strategies to obtain nanocomposites with superior properties and functionalities. While there is already significant research on the synthesis and characterizations of nanoparticles and hybrid nanocomposites, some research questions, such as how to design and control the interfacial morphology in polymer/nanoparticle hybrid nanocomposites, how to synthesize metal- organic framework (MOF) nanoparticles in well-defined and uniform …

Coulombic And Non-Coulombic Effects Of Single And Overlapping Electric Double Layers With Surface Charge Regulation, Raviteja Vangara

Chemical and Biological Engineering ETDs

The physical origin of charged interfaces involving electrolyte solutions is in the thermodynamic equilibrium between the surface reactive groups and certain dissolved ionic species in the bulk. This equilibrium is very strongly dependent on the precise local density of these species, also known as potential determining ions in the solution. The latter, however, is determined by the overall solution structure, which is dominated by the large number of solvent molecules relative to all solutes. Hence, the solvent contribution to the molecular structure is a crucial factor that determines the properties of electric double layers. Models that explicitly account for the …

An Investigation Of The Chemistry, Thermodynamics And Catalytic Activity Of Molybdenum Carbides, Shanti Kiran Nayak

Chemical and Biological Engineering ETDs

These studies investigate the chemistry and stability of molybdenum carbides as an electrocatalyst. Due to their unique electronic properties, molybdenum carbides are purposed as electrocatalysts for reaction systems such as hydrogen evolution reaction, bifunctional water splitting and CO oxidation.

In this study, various synthesis processes were utilized to produce different types of molybdenum carbide with varying properties of particle size, surface area and excess carbon. The samples characterized by XRD accompanied by Whole Profile Fitting, Electron Microscopy, Gas Adsorption (surface area) and XPS.

These synthesis processes were refined using fundamental thermodynamic analyses. These analyses highlight regions of stability of different …

Symmetry And Dopant Diffusion In Inverted Nanopyramid Arrays For Thin Crystalline Silicon Solar Cells, Seok Jun Han

Chemical and Biological Engineering ETDs

In this dissertation, we enhance the efficiency of thin flexible monocrystalline silicon solar cells by breaking symmetry in light trapping nanostructures and improving homogeneity in dopant concentration profile. These thin cells are potentially less expensive than conventional thick silicon cells by using less silicon material and making the cells more convenient to be handled when supported on polymer films. Moreover, these cells are widely applicable due to their flexibility and lightweight. However, for high efficiencies, these cells require effective light trapping and charge collection. We achieve these in cells based on 14-mm-thick free-standing silicon films with light-trapping arrays of nanopyramidal …

Fluid Transport In Porous Media For Engineering Applications, Eric M. Benner

Chemical and Biological Engineering ETDs

This doctoral dissertation presents three topics in modeling fluid transport through porous media used in engineering applications. The results provide insights into the design of fuel cell components, catalyst and drug delivery particles, and aluminum- based materials. Analytical and computational methods are utilized for the modeling of the systems of interest. Theoretical analysis of capillary-driven transport in porous media show that both geometric and evaporation effects significantly change the time dependent behavior of liquid imbibition and give a steady state flux into the medium. The evaporation–capillary number is significant in determining the time-dependent behavior of capillary flows in porous media. …

Cellular Modification And Artificial Cell Construction, Jimin Guo

Chemical and Biological Engineering ETDs

With all its complexities and different biofunctionalities, a cell is the basic structural and functional unit of all living organisms with the exception of viruses. In this dissertation, I demonstrated gain of function strategies of modifying mammalian cells using silicification and modular nanoparticle (NP) exoskeletons. In addition, I used a modular design concept to build a multifunctional artificial RBC system which can mimic the unique characteristics (e.g. shape, flexibility, the ability to carry oxygen, and long circulation times) of the native RBCs. Together, these cell modification or artificial cell construction strategies are expected to generate new mammalian cell-like structures with …

Metabolon-Inspired Design Of Multi-Modal Catalytic Cascade, Madelaine Seow Chavez

Chemical and Biological Engineering ETDs

Developing hybrid catalytic systems has been researched for the past decade in an effort to efficiently incorporate catalysts of different modalities in catalytic cascades. It has become imperative to design a cascade system where the catalysts are spatially organized to control the delivery of precursors, intermediates, and products. In this work, we have shown that a molecular catalyst, biocatalyst, and metallic catalyst can be co-localized using a carbonaceous support to create a hybrid catalytic system and complete the oxidation of oxalic acid to create a microchemical reactor. The molecular, pyrene-TEMPO catalyst oxidizes glyoxalic acid to oxalic acid. The enzyme oxalate …

Iron-Containing Nanoparticles For The Treatment Of Chrionic Biofilm Infections In Cystic Fibrosis, Leisha M. A. Martin

Nanoscience and Microsystems ETDs

Cystic fibrosis (CF) is the most common genetic disease resulting in the morbidity and mortality of Caucasian children and adults worldwide. Due to a genetic mutation resulting in malfunction of the Cystic Fibrosis Transmembrane Conductance Regulator (CFTR) protein, CF patients produce highly viscous mucus in their respiratory tract. This leads to impairment of the mucociliary clearance of inhaled microbes. In addition to reduced microbial clearance, anoxic environmental conditions in the lungs promote biofilm-mode growth of the pathogenic bacterial species Pseudomonas aeruginosa. Chronic infections of P. aeruginosa begin in early childhood and typically persist until respiratory failure and death result. The …

An Experimental And Numerical Investigation Of Flow Accelerated Flibe Corrosion, David B. Weitzel

Nuclear Engineering ETDs

Renewed interest in molten salt reactor technology has brought to light the need for a better understanding of FLiBe corrosion. To this end a flowing FLiBe corrosion test loop was designed to test the flow effects of FLiBe corrosion. The loop consists of a pump, melt tank, and stainless-steel tubing assembly that heats the molten salt to high temperatures and circulates it over test specimens. The experiment has been constructed and has completed initial shakedown testing.

To support the flowing FLiBe experiment, a numerical corrosion model that couples FLiBe electrochemistry, solid metal diffusion, and mass transport was implemented. The model …

Reaction Of Titanium Subhydride With Multiple Passivating Gasses, Erik C. Strobert Jr

Chemical and Biological Engineering ETDs

Sandia National Laboratories has used substoichiometric titanium hydride as a pyrotechnic fuel for decades. Production of titanium subhydride requires partial dehydriding of titanium hydride powder and subsequent chemical passivation to render the resultant bare titanium surface nonreactive and the powder non-pyrophoric. Novel passivation techniques, using a gas other than air, have been suggested in the past but have never been investigated. This work examines the reaction kinetics of titanium subhydride with three passivating agents, nitrogen, oxygen, and propane. These passivation experiments took place under isothermal conditions (420 ˚C) with varied dehydriding and passivation time periods. It was found that the …

The Endocytotic Fate Of A Mesoporous Silica Nanoparticle Supported Lipid Bylayer Crispr Delivery Vehicle, Angelea Maestas-Olguin

2019 Award Winners

No abstract provided.

Rate-Determining Step And Active Sites Probing For Platinum-Group-Metal Free Cathode Catalyst In Fuel Cell, Yechuan Chen

Chemical and Biological Engineering ETDs

With the increasing demand on renewable energy, the fuel cell has attracted more and more interests because of its large power density and controllable size. However, the insufficiency of element abundance and unstable expensive price of conventional platinum-based electrocatalysts used in anode and cathode makes it essential to find their substitutes. As one of the most promising candidates to be used in cathode for oxygen reduction reaction (ORR), iron-nitrogen-carbon (Fe-N-C) catalysts have been widely investigated and get commercialized recently, but still lacks comprehensive understanding on the kinetic mechanism.

This dissertation has been divided into three parts with a discussion on …

Controlled Nanomorphology Of Hybrid Organic/Inorganic Multi-Component Composites Through Cooperative Non-Covalent Interactions, Lingyao Meng

Shared Knowledge Conference

Hybrid organic–inorganic nanocomposite polymers, with inorganic nanoparticles embedded in organic matrix have emerged as a special category of multifunctional materials. With rational materials design, these hybrids can show the synergistic effect of the properties from both phases. Homogenous dispersion and orderly arrangement of the organic and inorganic components are key in their functionalities. By controlling the interface and corresponding interfacial interactions between the organic and inorganic entities, we have developed a logical approach to form stable and controlled hybrid nanofiber structures. We demonstrate the formation of hybrid polymer/quantum dots (or iron oxide nanoparticles) nanocomposites through non-covalent interactions (hydrogen bonding, ionic …

Spectro-Electrochemical Platforms For Dynamic Analyses Of Catalytic Cascade Systems, Nalin I. Andersen

Nanoscience and Microsystems ETDs

The development of spectro-electrochemical platforms that facilitate the dynamic analyses of complex catalytic cascade systems was explored in this research. These systems facilitated multiple modalities of catalysts and were used as platforms for monitoring catalytic transformations quasi-in situ. The analytical platforms allowed for the characterization of intermediates and products using surface-enhanced Raman spectroscopy (SERS). The design and fabrication of these devices proved to be reproducible, made of materials that can be manipulated for multiple applications, and incorporate fluid mechanics, electrochemistry, and multimodal catalysis. Microfluidic technology offers capabilities for understanding catalytic cascade systems by providing precise dynamic control of …

An Investigation Of The Effects Of The Second Pyrolysis On The Chemistry, Morphology, And Performance Of Iron-Nicarbazin Catalysts, Elizabeth B. Weiler

Chemical and Biological Engineering ETDs

Proton exchange membrane fuel cells offer a cost-effective, environmentally friendly, and sustainable alternative to petroleum-based power sources to the transportation sector. However, slow electrochemical reactions at the cathode of these fuel cell prevent the technology from being competitive. Iron-nitrogen-carbon based catalysts have emerged as a viable answer to this problem, yet further progress is needed to improve their performance beyond that of current state-of-the-art platinum-based catalysts, which are economically and geopolitically impractical to be a final solution. Currently, a two-step high temperature pyrolysis method has proven a promising way to synthesize iron-nitrogen-carbon catalysts for optimized performance, but there is a …

Anodic Catalysts For Anion Exchange Membrane Fuel Cells, Aaron Joseph Roy

Chemical and Biological Engineering ETDs

With a limited availability of energy resources from petroleum and other fossil fuels, as well as growing concerns relating to the environmental implications of fossil fuel emissions, non-carbon fuels which can be utilized in proton and anion exchange membrane fuel cells (PEMFC’s/AEMFC’s), such as hydrogen and hydrazine hydrate (HH), are becoming more attractive as alternative fuels. Historically, platinum and platinum group metal catalysts (PGM) have been used as cathode and anode catalyst materials for both PEMFC’s and AEMFC’s. Although these catalysts are the highest performing catalysts available for the conversion of hydrogen energy in fuel cells, the limited availability and …

Microbial Desalination Cells With Efficient Platinum Group Metal-Free Cathode Catalysts, Morteza Rezaei Talarposhti

Chemical and Biological Engineering ETDs

Iron-nitrogen-carbon based catalyst was used at the cathode of a microbial desalination cell (MDC) and compared with platinum (Pt) and activated carbon (AC) cathode. Fe-N-C catalyst was prepared using nicarbazin (NCB) as organic precursor by sacrificial support method (SSM). Rotating ring disk electrode (RRDE) experiments shows that Fe-NCB had higher electrocatalytic activity compared to AC and Pt. The utilization of Fe-NCB into the cathode improved substantially the performance output with initial maximum power density of 49±2 μWcm^-2 in contrast to Pt and AC catalysts which have shown lower values of 34±1 μWcm^-2 and 23.5±1.5 μWcm^-2, respectively. …

Incorporation Of Catalytic Modalities For Forming Of A Catalytic Cascade, Albert T. Perry Iii

Nanoscience and Microsystems ETDs

This dissertation investigates the novel incorporation of inorganic and enzymatic catalysts. There is little literature on inorganic catalysts operating at biologically relevant pHs and as such a significant amount of this dissertation focuses on determination of catalyst activity. Mn amino-anitpyrene (MnAAPyr), Pt, Pt alloys, Mn-N-C and Pd catalysts on 3D graphene supports(3D-GNS), were explored for activity towards glycerol intermediates: oxalic acid, mesoxalic acid, glyoxalic acid, and formic acid. MnAAPyr was designed to mimic the reaction center of oxalate decarboxylase and oxalate oxidaze, the natural catalyst towards oxalic acid. It showed high activity towards oxalic acid, with onset potentials of 0.714±0.002V …

Designing Nanocomposite Materials For Catalyzing Electrochemical Reactions In Anion Exchange Membrane Fuel Cells, Sadia Afrin Kabir

Chemical and Biological Engineering ETDs

Fuel cells are considered to be one the most promising sustainable energy technologies for energy conversion and electric power generation. With the development of stable, conductive and high performance anion exchange membranes and ionomers, there has been an increased interest towards studying various electrochemical reactions in Anion Exchange Membrane Fuel Cells (AEMFC). This increased attention has been attributed to the comparatively facile reaction kinetics, minimized corrosion effects and reduced fuel crossover in alkaline media. However, the oxygen reduction reactions (ORR) taking place in the cathode compartment of fuel cells plays a crucial role in optimizing the electrochemical energy conversion efficiency, …

Ion Size Effects On The Properties Of Charge Regulating Electric Double Layers, Divya Jyoti Prakash

Nanoscience and Microsystems ETDs

The behavior of charged interfaces formed in various systems like colloidal solution, fuel cells, battery, electro-deposition, catalysis is governed by the properties of electrical double layer(EDL). Civilized model with charge regulation boundary condition determined by thermodynamic equilibrium at the interface has been used to model electrical double layer and shows that size of the solvent plays a critical role in characterizing the properties of EDL using classical density functional theory.This thesis investigates the impact of ion size in electrolyte solutions on the electrical double layer formed at the interface using a similar model. It is found that ion size greatly …

Graphite And Graphene-Oxide Based Pgm-Free Model Catalysts For The Oxygen Reduction Reaction, Joseph Henry Dumont

Nanoscience and Microsystems ETDs

The world currently relies heavily on fossil fuels such as coal, oil, and natural gas for its energy. Fossil fuels are non-renewable, that is, they draw on finite resources that will eventually dwindle, becoming too expensive or too environmentally damaging to retrieve. One alternative source of energy are fuel cells, electrochemical devices that convert chemical energy to cleanly and efficiently produce electricity. They can be used in a wide range of applications, including transportation, stationary, portable and emergency power sources. Their development has been slowed by the high cost of PGM electrocatalysts needed at both electrodes as well as sluggish …