Engineering Commons^™

The Characterization And Nanomechanical Properties Of Microstructurally Complex Systems, Kerry Ann Baker

Theses and Dissertations--Chemical and Materials Engineering

Since the dawn of civilization, the use of metals has played an integral role in the evolution of human society. Over the years, and with the introduction of new engineering and science, we have learned how to combine metals to create new metallic systems. We have expanded our understanding of dealloying and chemical reactions, and, in doing so, we created nanoporous metals. Our use of metals has evolved from basic alloys such as bronze and steel to more complex alloys such as multi-principal element alloys. Nanoporous gold is an advanced metallic system that can be created through the dealloying process. …

Thermomechanical Process Simulation And Quantification Of Nanoscale Precipitation Influencing Ductility And Strength During Alloy Processing, Alyssa Stubbers

Theses and Dissertations--Chemical and Materials Engineering

Experimental process simulation and quantification of microstructure development during processing are challenging due to limitations with machinery temperature capability, inadequate resolution and sampling volume of currently available characterization techniques, and difficulty characterizing material microstructures as close to processing-relevant conditions as possible. This dissertation addresses how process simulation can be performed using Gleeble thermomechanical technologies and how microstructure development during these processing simulations can be quantified both in-situ and ex-situ.

The first portion of this dissertation demonstrates how Gleeble technologies can be applied to simulate complex material processing conditions in order to produce process-property profiles that can be used to inform …

Application Of Multi-Scale Computational Techniques To Complex Materials Systems, Mujan N. Seif

Theses and Dissertations--Chemical and Materials Engineering

The applications of computational materials science are ever-increasing, connecting fields far beyond traditional subfields in materials science. This dissertation demonstrates the broad scope of multi-scale computational techniques by investigating multiple unrelated complex material systems, namely scandate thermionic cathodes and the metallic foam component of micrometeoroid and orbital debris (MMOD) shielding. Sc-containing "scandate" cathodes have been widely reported to exhibit superior properties compared to previous thermionic cathodes; however, knowledge of their precise operating mechanism remains elusive. Here, quantum mechanical calculations were utilized to map the phase space of stable, highly-faceted and chemically-complex W nanoparticles, accounting for both finite temperature and chemical …

Surface Properties, Work Function, And Thermionic Electron Emission Characterization Of Materials For Next-Generation Dispenser Cathodes, Antonio Mantica

Theses and Dissertations--Chemical and Materials Engineering

A dispenser cathode’s ability to thermionically emit electrons is highly dependent on its material properties, especially those of the surface. Understanding the relationship between surface properties and electron emission, therefore, is vital to reach the next generation of the many vacuum electron devices (VEDs) that rely on the physics of electron emission. In the past century, many techniques have been developed to characterize material surfaces and quantify thermionic emission. These techniques are based on a wide range of different physical phenomena, including measuring photoemission via the photoelectric effect, measuring the electrostatic potential between metals in electrical contact, and current collection …

Drop Wetting And Sliding On Soft, Swollen Elastomers, Zhuoyun Cai

Theses and Dissertations--Chemical and Materials Engineering

Soft, slippery surfaces have gained increasing attention due to their wide range of potential applications, for example in self-cleaning, anti-fouling, liquid collection, and more. One design approach in creating slippery surfaces is using a swollen elastomer, which is a polymer network swollen with a lubricant. This type of surface may be beneficial for longer-term use than standard lubricant-infused surfaces, and provides a versatile surface with tunable mechanical properties. Hence, understanding the physics of soft surface interactions is important for fundamental soft matter physics, biomaterials, adhesives, and coatings. This research experimentally investigates wetting on soft infused networks, with the aim of …

Effects Of Confinement On Ionic Liquids And Deep Eutectic Solvents For The Design Of Catalytic Systems, Electrochemical Devices, And Separations, Andrew Drake

Theses and Dissertations--Chemical and Materials Engineering

Confinement of ionic liquids (ILs) and deep eutectic solvents (DESs) within mesoporous materials such as silica helps to control the local environment within the pores for applications such as catalysis, electrochemistry, and absorption. Silica thin films with 2.5 and 8 nm pores and micron-sized silica particles with pore diameters of 5.4 and 9 nm were synthesized to study the effect of nanoconfinement on ILs 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF₆]), 1-butyl-3-methylimidazolium chloride ([BMIM][Cl]), and DESs reline and ethaline (choline chloride and urea or ethylene glycol). Silica thin films with vertically aligned, well ordered, and accessible pores were synthesized via the evaporation-induced …

Improving Manufacturing Processes For Making Lithium Ion Battery Electrodes, Ming Wang

Theses and Dissertations--Chemical and Materials Engineering

Rechargeable lithium-ion batteries (LIBs) are widely used to provide energy and power in portable electronics, electric vehicles, and energy storage systems. The LIB market has grown dramatically as they have a combination of high energy density, high power density, proven reliability, and long cycle life. The manufacturing process is one of the key factors as it strongly affects the cost and performance of LIBs.

This dissertation is focused firstly on the development of a conventional slurry-based electrode manufacturing process. Slurry making is a critical step that affects the subsequent steps in battery manufacturing. In this work, we have investigated the …

An Electrochemical-Mechanical Investigation Of Next Generation Lithium Metal Electrode And Solid Electrolyte, Andrew Meyer

Theses and Dissertations--Chemical and Materials Engineering

Lithium-ion batteries (LIBs) are a staple in today’s society. From our cellphones, laptops, power tools, the ever-growing electric vehicle, and many more application, LIBs are more important to us than most realize. They provide the best combination of both high-energy and high-power density compared to other battery types such as Ni-Cd, Ni-MH, or the lead acid batteries used in our cars. Plus, LIBs are much safer. However, as new technologies grow and are developed, the demand for higher energy and power density, better safety, lower costs, and longer life increases. One way to achieve the ever-increasing demands is to replace …

A Computational Exploration Of The Scandate Cathode Surface, Shankar Miller-Murthy

Theses and Dissertations--Chemical and Materials Engineering

The exact surface configuration of scandate cathodes has been a point of contention for the materials community for a long time. Without proper understanding of it and the related structures and emission mechanisms, scandate cathodes remain patchy and unreliable emitters. Thus, density functional theory techniques were applied to various potential surface arrangements and found that there are several low-energy surfaces with low work functions that incorporate a scandium interlayer between tungsten and oxygen or otherwise have a scandium-on-tungsten structure. Furthermore, it was discovered that adding a monolayer of scandium directly to a tungsten surface is surprisingly favorable, thermodynamically. While none …

Pitch-Based Carbon Fiber Derived From Coal Extract Liquids, Cierra Danielle Crowe

Theses and Dissertations--Chemical and Materials Engineering

Limited coal coking operations and the use of coal-tar pitch as a binding agent in the production of metallurgical anodes has led to a limited availability of coal tar pitch for carbon fiber products. This has sparked interest in utilizing non-metallurgical coal-based liquids as an alternative to traditional coal tar from metcoke operations. This can be achieved by low severity solvent extraction, with heavy aromatic solvents, to produce coal liquids that act as precursor to pitch-based carbon fiber. This thesis aims to establish the processing and determine the impact of utilizing coal liquids to produce carbon fiber. In this work …

Green-Route Synthesis Of Halide Perovskite Materials And Their Optoelectronic Properties, Xiaobing Tang

Theses and Dissertations--Chemical and Materials Engineering

Colloidal semiconductor quantum dots (QDs), also called as nanocrystals (NCs), are a class of functional materials with extraordinary properties, which are different from their bulk counterparts and benefit from their exclusive quantum confinement (size) effect. Semiconductor exhibits the quantum confinement effect when the characteristic size of the semiconductor is comparable to or smaller than the de Broglie wavelength of the electron wave function and/or the exciton Bohr diameter of the bulk semiconductor. In recent years, metal halide perovskite NCs, as next-generation semiconductor materials for lighting and display, have aroused a wide attention due to their excellent optoelectronic properties. However, traditional …

Derivation, Exploration And Evaluation Of Non-Equiatomic High Entropy Alloys, Artashes Ter-Isahakyan

Theses and Dissertations--Chemical and Materials Engineering

High-entropy alloys (HEAs) are a class of multicomponent alloys based on an innovative alloying strategy that employs multi-principle elements in relatively high concentrations. Commonly defined as alloys that contain at least five principal elements, each with a concentration between 5 and 35 at %. The term entropy refers to the excess configurational entropy associated with HEAs, which is thought to facilitate the formation of solid solutions. The design strategy results in vast compositional space for exploration and innovative potential triggering a renaissance in physical metallurgy. These alloys may have favorable properties compared to conventional dilute solid solutions, but their preeminent …

Microscale Contact And Friction Of Low Modulus, Lightly Crosslinked Polydimethylsiloxane, Justin Glover

Theses and Dissertations--Chemical and Materials Engineering

Friction and adhesion of soft materials are important for pressure sensitive adhesives, biomaterials, and soft robotics; however, the behavior on the microscale is not fully understood. When two objects come into contact, their interactions are usually mediated by small contact points due to surface roughness. At the microscale size, surface forces can deform soft materials to minimize energy by increasing the contact area, which is balanced by the elastic deformation of the polymer network. However, for soft, crosslinked materials with a modulus below ~100 kPa, it is challenging to predict the behavior with prior contact and friction models. Additionally, lightly …

Fabrication Of Nanoporous Materials For Applications Under Extreme Environments, Maria Kosmidou

Theses and Dissertations--Chemical and Materials Engineering

The study of nanoporous materials has become a key aspect of nanotechnology due to their high surface-area-to-volume ratio, arising from the small size ligaments and pores that form the structure. Sensing, catalysis, micro-electromechanical systems (MEMS), medical applications, and materials for radiation environments are some of the applications for which nanoporous materials are considered great candidates. This work, performed at the Ion Beam Laboratory (IBL) at Sandia National Laboratories (SNL), examines the effect of heavy and light ion irradiation exposure on nanoporous Au. Radiation damage accumulation is observed with real-time recording of the creation, migration, and removal of the radiation-induced defects …

Tailoring Thermoresponsive Poly(N-Isopropylacrylamide) Toward Sensing Perfluoroalkyl Acids, Dustin Thomas Savage

Theses and Dissertations--Chemical and Materials Engineering

Widespread distribution of poly- and perfluoroalkyl substances (PFAS) in the environment combined with concerns for their potentially negative health effects has motivated regulators to establish strict standards for their surveillance. The United States Environmental Protection Agency issued a cumulative domestic threshold of 70 ppt for water supplies, and this bar is even lower in some local districts and other countries. Monitoring PFAS consequently requires sensitive analytical equipment to meet regulatory specifications, and liquid chromatography with tandem mass spectroscopy (LC/MS/MS) is the most common technique used to satisfy these requirements. Though extremely sensitive, the instrument is often burdened by pretreatment regimens, …

Electrochemical Performance Of Biomass-Derived Activated Carbon Supercapacitor Under Compression, Yulin Zhang

Theses and Dissertations--Chemical and Materials Engineering

Supercapacitors are important energy storage device of high-power density, fast charge/discharge rate, environmental friendliness and long service life. Currently, flexible supercapacitors have attracted widespread interest in academia and industry. Supercapacitors under the action of external force will inevitably cause structural changes, performance degradation and even loss of energy storage and supply functionalities. As the most abundant renewable resource so far, biomass is an important energy source for human survival and development. Most electrode materials for supercapacitors are porous activated carbons, which can be derived from abundant renewable biomass, contributing to the sustainable development of society and environmental protection. This thesis …

The Development Of Structural Hollow Carbon Fibers From A Multifilament Segmented Arc Spinneret: Precursors, Oxidation, And Carbonization, Elizabeth Ashley Morris

Theses and Dissertations--Chemical and Materials Engineering

Carbon fiber is an ideal material for structural applications requiring high strength and stiffness and low weight. Yet it has seen only incremental improvements in properties over the last few decades. Carbon fibers remain limited in attaining their theoretical tensile strength and modulus, largely due to defects in their structure, some of which stem from the fiber production process itself. Through the mitigation of defect formation as well as approaches to decrease fiber linear density, it is hypothesized that carbon fiber with enhanced specific properties, including specific strength and modulus, could be produced which would significantly propel its unique capabilities. …

Effects Of Hole Transporting Layers And Surface Ligands On Interface Energetics And Photovoltaic Performance Of Methylammonium Lead Iodide Perovskites, So Min Park

Theses and Dissertations--Chemical and Materials Engineering

Organic metal halide perovskites are promising materials for various optoelectronic device applications such as light emitting diodes (LED) and photovoltaic (PV) cells. Perovskite solar cells (PSCs) have shown dramatic increases in power conversion efficiency over the previous ten years, far exceeding the rate of improvement of all other PV technologies. PSCs have attracted significant attention due to their strong absorbance throughout the visible region, high charge carrier mobilities, color tunability, and ability to make ultralight weight devices. However, organic metal halide perovskites still face several challenges. For example, their environmental stability issue must be overcome to enable widespread commercialization. Meeting …

Fabrication, Characterization And Applications Of Highly Conductive Wet-Spun Pedot:Pss Fibers, Ruben Sarabia Riquelme

Theses and Dissertations--Chemical and Materials Engineering

Smart electronic textiles cross conventional uses to include functionalities such as light emission, health monitoring, climate control, sensing, storage and conversion of energy, etc. New fibers and yarns that are electrically conductive and mechanically robust are needed as fundamental building blocks for these next generation textiles.

Conjugated polymers are promising candidates in the field of electronic textiles because they are made of earth-abundant, inexpensive elements, have good mechanical properties and flexibility, and can be processed using low-cost large-scale solution processing methods. Currently, the main method to fabricate electrically conductive fibers or yarns from conjugated polymers is the deposition of the …

Nanostructured Metal Thin Films As Components Of Composite Membranes For Separations And Catalysis, Michael J. Detisch

Theses and Dissertations--Chemical and Materials Engineering

Novel metallic thin film composite membranes are synthesized and evaluated in this work for improved separations and catalysis capabilities. Advances in technology that allow for improved membrane performance in solvent separations are desirable for low molecular weight organic separation applications such as those in pharmaceutical industries. Additionally, the introduction of catalytic materials into membrane systems allow for optimization of complex processes in a single step. By adding a nanostructured metallic thin film to its surface, a polymer membrane may be modified to exhibit these improved properties. Using magnetron sputtering, thin metal films may be deposited on commercially available membranes to …

Ab Initio Investigation On The Surface Chemistry Of Functionalized Titania Membranes, Evan Hyde

Theses and Dissertations--Chemical and Materials Engineering

Titania (titanium dioxide) is a metal oxide which has recently been investigated as a photocatalyst, most commonly for use in hydrolysis, which absorbs mostly in the UV range. However, the range of absorption can be shifted to fall within the visible light range either by doping or by functionalizing the surface with atomic or molecular adsorbates. Over the course of this research, a series of Density Functional Theory (DFT) calculations are performed to ascertain the effects of these different methods on the photocatalytic performance of titania. While the effects of nitrogen doping and oxygen vacancies are well known, more recent …

Understanding And Mitigating The Electrochemical-Mechanical Degradation Of High Capacity Battery Electrodes, Dingying Dang

Theses and Dissertations--Chemical and Materials Engineering

Lithium-ion batteries (LIBs) with high energy density and cycling stability play a critical role in developing electric vehicle (EV) and grid energy storage techniques. The electrochemical performance of LIBs can be improved by using high capacity positive (e.g., LiNi_1/3Mn_1/3Co_1/3O₂, i.e., NMC111) and negative (e.g., silicon) electrodes; both, however, experience severe electrochemical-mechanical degradation caused by the lithiation/delithiation induced volume changes. Understanding mechanical degradation mechanisms and their relationships with the capacity fading of electrodes is important for improving the cycling stability of electrodes as well as optimizing the design of electrodes with high capacity …

Biomass-Derived Activated Carbons For Electrical Double Layer Supercapacitors: Performance And Stress Effect, Wenxin Cao

Theses and Dissertations--Chemical and Materials Engineering

The vigorous development of human civilization has significantly increased the energy consumption in recent years. There is a great need to use renewable energy sources to substitute the depleting traditional fossil fuels, such as crude oil, natural gas and coal. The development of low-cost and high-performance energy storage devices (ESDs) and systems have drawn great attention due to their feasibility as backup power supply and their applications in portable electronics and electric vehicles. Supercapacitors are among the most important ESDs because of their long charging-discharging cycle life, high power capability and a large operating temperature range. In this thesis, high-performance …

Mechanical Properties And Degradation Of High Capacity Battery Electrodes: Fundamental Understanding And Coping Strategies, Yikai Wang

Theses and Dissertations--Chemical and Materials Engineering

Rechargeable lithium ion and lithium (Li) metal batteries with high energy density and stability are in high demand for the development of electric vehicles and smart grids. Intensive efforts have been devoted to developing high capacity battery electrodes. However, the known high capacity electrode materials experience fast capacity fading and have limited cycle life due to electromechanical degradations, such as fracture of Si-based electrodes and dendrite growth in Li metal electrodes. A fundamental understanding of electromechanical degradation mechanisms of high capacity electrodes will provide insights into strategies for improving their electrochemical performance. Thus, this dissertation focuses on mechanical properties, microstructure …

The Study Of Scandate Cathode And Its Characterization Under Various Stages Of Processing, Xiaomeng Zhang

Theses and Dissertations--Chemical and Materials Engineering

Scandate cathode under various processing stages: scandia nano-powder, tungsten scandia mix powder, sintered and impregnated pellets, were characterized with techniques that included electron microscopy, EDS, XPS, and work function measurements. The size and shape uniformity of nano-scale scandia particles changed from round to square and polyhedron during heat treatment. Reduction in size and improvement in size uniformity as heat treating temperature increased were observed. When determining the highest Sc coverage, three assessment methods were used and with their combined results, it was concluded that set VII had the highest Sc at%. In the sintered pellets, it was observed with SEM …

Investigation Of Transition-Metal Ions In The Nickel-Rich Layered Positive Electrode Materials For Lithium-Ion Batteries, Shuang Gao

Theses and Dissertations--Chemical and Materials Engineering

Layered lithium transition-metal oxides (LMOs) are used as the positive electrode material in rechargeable lithium-ion batteries. Because transition metals undergo redox reactions when lithium ions intercalate in and disintercalate from the lattice, the selection and composition of transition metals largely influence the electrochemical performance of LMOs. Recently, a Ni-rich compound, LiNi_0.8Co_0.1Mn_0.1O₂ (NCM811), has drawn much attention. It is expected to replace its state-of-the-art cousins, LiCoO₂ (LCO) and LiNi_1/3Co_1/3Mn_1/3O₂ (NCM111), because of its higher capacity, lower cost, and reduced toxicity. However, the excess Ni, as a …

Understanding The Structure-Property-Performance Relationship Of Silicon Negative Electrodes, Jiazhi Hu

Theses and Dissertations--Chemical and Materials Engineering

Rechargeable lithium ion batteries (LIBs) have long been used to power not only portable devices, e.g., mobile phones and laptops, but also large scale systems, e.g., electrical grid and electric vehicles. To meet the ever increasing demand for renewable energy storage, tremendous efforts have been devoted to improving the energy/power density of LIBs. Known for its high theoretical capacity (4200 mAh/g), silicon has been considered as one of the most promising negative electrode materials for high-energy-density LIBs. However, diffusion-induced stresses can cause fracture and, consequently, rapid degradation in the electrochemical performance of Si-based negative electrodes. To mitigate the detrimental effects …

Nanoharvesting And Delivery Of Bioactive Materials Using Engineered Silica Nanoparticles, Md Arif Khan

Theses and Dissertations--Chemical and Materials Engineering

Mesoporous silica nanoparticles (MSNPs) possess large surface areas and ample pore space that can be readily modified with specific functional groups for targeted binding of bioactive materials to be transported through cellular barriers. Engineered silica nanoparticles (ESNP) have been used extensively to deliver bio-active materials to target intracellular sites, including as non-viral vectors for nucleic acid (DNA/RNA) delivery such as for siRNA induced interference. The reverse process guided by the same principles is called “nanoharvesting”, where valuable biomolecules are carried out and separated from living and functioning organisms using nano-carriers. This dissertation focuses on ESNP design principles for both applications. …

Characterization Of Nanostructure, Materials, And Electron Emission Performance Of Next-Generation Thermionic Scandate Cathodes, Xiaotao Liu

Theses and Dissertations--Chemical and Materials Engineering

Scandate cathodes, where scandia is added to the tungsten cathode pellets, have recently received substantial and renewed research interest owing to significantly improved electron emission capabilities at lower temperatures, as compared with conventional dispenser cathodes. However, there are several persistent issues including non-uniform electron emission, lack of understanding regarding scandium’s role in the emission mechanism, and unreliable reproducibility in terms of scandate cathode fabrication. As a result, scandate cathodes have not yet been widely implemented in actual vacuum electron devices (VEDs).

The surface structure and chemical composition of multiple scandate cathodes – prepared with the powder using the liquid-solid (L-S) …

Synthesis, Design, And Evaluation Of The Fluorescent Detection Of Polychlorinated Biphenyls(Pcbs) In Aqueous System, Irfan Ahmad

Theses and Dissertations--Chemical and Materials Engineering

The exposure to halogenated persistent organic pollutants (POPs), such as polychlorinated biphenyls (PCBs), has been linked to numerous inflammatory diseases, including diabetes, cancer and lowered immune response. PCBs have low solubility in water, and they interact with other contaminants, making their detection quite challenging. While, there have been several attempts at improving the ease of detection and sensing of PCBs, gas chromatography-mass spectrometry (GC-MS) remains the gold standard. However, despite its ubiquitous use, GC-MS is a challenging technique that requires high skill and careful sample preparation, which are time-consuming and costly. As such, there is still a need to develop …