Materials Science and Engineering Commons^™

Towards Completely Automated Glycan Synthesis, Matteo Panza

Dissertations

Carbohydrates are ubiquitous both in nature as biologically active compounds and in medicine as pharmaceuticals. Although there has been continued interest in the synthesis of carbohydrates, chemical methods require specialized knowledge and hence remain cumbersome. The need for development of rapid, efficient and operationally simple procedures has come to the fore. This dissertation focuses on the development of a fully automated platform that will enable both experts and non-specialists to perform the synthesis of glycans. Existing automated methods for the synthesis of oligosaccharides are highly sophisticated, operationally complex, and require significant user know-how. By contrast, high performance liquid chromatography (HPLC) …

Improving Boron For Combustion Applications, Kerri-Lee Annique Chintersingh

Dissertations

Boron has received much attention as a potential additive to explosives and propellants due to its high theoretical gravimetric and volumetric heating values. The challenge, however, is that boron particles tend to agglomerate, have lengthy ignition delays and very low combustion rates. Prior research indicates that boron’s long ignition delays are due to its inhibiting naturally occurring oxide layer, impeding the diffusion of reactants for oxidation. For combustion, current studies report that boron particles have two consecutive stages, but the actual reaction mechanism is poorly understood. Despite many years of relevant research, quantitative combustion data on micron-sized boron particles are …

Supercapacitors With Gate Electrodes, Tazima Selim Chowdhury

Dissertations

A new approach to improve the capacitance of supercapacitors (SC) is proposed in this study. A typical SC is composed of an anode and a cathode; a separator in between them assures an unintentional discharge of the capacitor. The study focuses on a family of structured separators, either electronically active or passive which are called gates. An active structured separator layer has been fabricated and analyzed. The structured separator has characteristics of electrical diode and is fabricated out of functionalized carbon nanotubes (CNT). Improvement of the overall capacitance of SC, equipped with either active or passive structured separators demonstrated a …

Epitaxial Growth Of Iii-Nitride Nanostructures And Their Optoelectronic Applications, Moab Rajan Philip

Dissertations

Light-emitting diodes (LEDs) using III-nitride nanowire heterostructures have been intensively studied as promising candidates for future phosphor-free solid-state lighting and full-color displays. Compared to conventional GaN-based planar LEDs, III-nitride nanowire LEDs exhibit numerous advantages including greatly reduced dislocation densities, polarization fields, and quantum-confined Stark effect due to the effective lateral stress relaxation, promising high efficiency full-color LEDs. Beside these advantages, however, several factors have been identified as the limiting factors for further enhancing the nanowire LED quantum efficiency and light output power. Some of the most probable causes have been identified as due to the lack of carrier confinement in …

N8- Polynitrogen Stabilized On Carbon-Based Supports As Metal-Free Electrocatalyst For Oxygen Reduction Reaction In Fuel Cells, Zhenhua Yao

Dissertations

The sluggish oxygen reduction reaction (ORR) kinetics at the cathode is one of the key factors limiting the performance of polymer electrolyte membrane fuel cell (PEMFC). Platinum-based materials are the most widely studied catalysts for this ORR reaction while their large-scale practical application in fuel cells is hindered due to their scarcity and low stability. Therefore, highly active, low cost and robust non-Pt catalysts are being developed to overcome the drawbacks. Recently, a novel polynitrogen N8- (PN) stabilized on multiwall carbon nanotube (MWNT) was synthesized under ambient condition for the first time by our group and demonstrated high ORR activities. …

Surface-Enhanced Raman Detection Of Glucose On Several Novel Substrates For Biosensing Applications, Laila Saad Alqarni

Dissertations

The small normal Raman cross-section of glucose is considered to be a major challenge for its detection by Surface Enhanced Raman Spectroscopy (SERS) for medical applications. These applications include blood glucose level monitoring of diabetic patients and evaluation of patients with other medical conditions, since glucose is a marker for many human diseases. This dissertation focuses on Surface-Enhanced Raman Scattering primarily for the detection of glucose. Some experiments also are carried out for the detection of the corresponding enzyme glucose oxidase that is used in electrochemical glucose sensors and in biofuel cells. This project explores the possibility of utilizing Surface …

“Polysoaps” Via Raft Copolymerization To Form Well-Defined Micelles For Water Remediation And Targeted Drug Delivery Applications, Phillip Pickett

Dissertations

Amphiphilic copolymers have become increasingly important for environmental and biological applications due to their behavioral characteristics in aqueous solution. For example, structurally-tailored statistical amphiphilic copolymers or “polysoaps” can self-assemble into micelles or other architectures in water at various concentrations. Polysoaps may be differentiated from small molecule surfactant micelles in their capability to self-assemble into unimolecular associates (unimolecular micelles) with no dependence on concentration. Such micelles offer enormous potential for dispersion of hydrophobic species in water at high dilution. Importantly, each polymer chain forms its own micelle and upon dilution, these micelles remain intact and capable of dispersing hydrocarbon material in …

Engineering Multifunctional And Morphologically Diverse Polymer Brush Surfaces, Cassandra M. Reese

Dissertations

The combination of surface-initiated polymerization (SIP) and post-polymerization (PPM) serves as a powerful approach to fabricate complex, multifunctional polymer films, which can be precisely tuned for desired surface engineering applications. Careful manipulation of PPM parameters such as reaction conditions, the tethered brush parameters, and the physical properties of the unbound post-modifier greatly influence the depth of penetration of the post-modifier and the polymer brush compositional heterogeneity. This dissertation focuses on engineering polymer brush surfaces with multifunctional chemistries and tunable morphologies by investigating the PPM parameters that dictate the distribution of post-modifiers on grafted polymer brush surfaces.

The first chapter of …

Magnetic Field Assisted Milli-Scale Robotic Assembly Machine: An Approach To Massively Parallel Swarm Robotic Automation Systems, Yan Liu

Dissertations

The vision of highly parallel, automated manufacturing systems that can build macroscopic products by heterogeneous assembly of many small devices will have a major impact in manufacturing. In this study, a novel milli-scale robotic assembly machine with parallel capabilities, assisted with programmable magnetic field, is developed. The machine prototype consists of a 16x16 array of electromagnets. The dimensions of the electromagnets are 5mm high with an inner diameter of 1.1mm and outer diameter of 2.5mm. All the electromagnets are driven by a 16x16 array of H-Bridges, and an Arduino microcontroller is used to control and program the arrays.

Using the …

Development Of Flexible Nickel-Zinc And Nickel-Iron Batteries, Xianyang Meng

Dissertations

The fabrication of flexible nickel-zinc batteries using a facile mixing of electroactive components for electrode preparation is presented. Polytetrafluoroethylene (PTFE) is found to be an effective binder by reducing concentration polarization, providing chemical/physical stability and enhancing flexibility. The zinc electrode containing PTFE maintains its original porous morphology even after hundreds of cycles while polymers such as PEO show morphology change. Each component, as well as the assembled flexible cells show desired flexibility and stability even under bending conditions.

The fabrication of flexible nickel-iron batteries using printable composite electrodes embedded with multiwalled carbon nanotubes (CNT) is also presented. All the metal …

Polyhedral Oligomeric Silsesquioxane-Phosphate Glass Matrix Nanocomposites With Additional Chapter On Phosphate Glass-Poly(Ethylene Terephthalate) Matrix Composites, Kyoungtae Kim

Dissertations

Preparation and characterization of tin fluorophosphate glass (Pglass) matrix nanocomposites incorporating polyhedral oligomeric silsesquioxane (POSS) were investigated on the structural, thermal, morphological, mechanical, and rheological properties. Various processes including synthesis, extrusion and sintering processes were applied to prepare the nanocomposite samples. Another application of POSS with hydrophobic functional groups on the well-structured nanoscale silicate cage with three silanol groups was investigated to present the feasibility to use POSS molecule as a coating material on the surface of the hydrophilic inorganic glass. In addition, Poly(ethylene terephthalate) polymer matrix composites incorporating Pglass was studied to present the benefits of the Pglass with …

Hydrogen Bond Mediated Water Structuring, Diffusion, And Elastic Properties In Acrylamide Copolymer Glycohydrogels, April Levu Fogel

Dissertations

Glycohydrogels have recently gained considerable interest as biocompatible and high water content hydrogels that have similar physicochemical nature to the cell membrane, making them ideal materials for targeted biomedical and personal care applications (e.g., drug delivery systems, biosensors, and contact lenses). Regardless of the specific application, water-polymer and water-water hydrogen bonding interactions have been shown to dictate hydration stability and diffusional properties in traditional hydrogel architectures (e.g., crosslinked HEMA). However, due to the development of glycohydrogel materials within the past two decades, most literature focuses on synthetic techniques and general hydration characteristics. Furthermore, scant literature examines the effect of hydrophobically …

Cellulose-Derived Glycosaminoglycan Mimetic For Use In Cartilage Tissue Engineering Strategies, Roseline Dominic Menezes

Dissertations

Articular cartilage has limited healing and self-repair capability due to the absence of vasculature, lymphatic vessels, and nerves. Damage to articular cartilage becomes irreversible leading to formation of osteoarthritis that could severely degrade a person's quality of life. Approximately, 5-10% of cartilage tissue is made up of glycosaminoglycans (GAG), which sequester growth factors as well as provide structural integrity to the native cartilage tissue. Transforming growth factor-beta3 (TGF-β3) is an important growth factor for inducing chondrogenesis in mesenchymal stem cells (MSCs). Bioavailability of TGF-β3 plays a critical role in cartilage repair both in vitro and in vivo. This study evaluates …

Silicon Based Uncooled Microbolometer, Asahel Banobre

Dissertations

During the last decade, uncooled microbolometer infrared detectors have attracted the attention of military and civilian infrared detection and imaging industry due to their significant advantages. In actuality, infrared imaging systems play a critical role in sectors such as thermography (predictive maintenance and building inspection), commercial and civilian applications (vision automotive, surveillance, navigation and fire-fighting), and defense industry (thermal weapon sight, soldier vision and vehicle vision enhancer). Compared with the cryogenically cooled infrared photon detectors, uncooled infrared imaging technology offers advantages such as operation at room temperature, light weight and size, reduced power consumption, easy integration with read-out electronics and …

Structural Studies To Determine The Mechanisms Supporting Multiferroic And Ferroelectric Properties Of Complex Oxides, Han Zhang

Dissertations

Multiferroics are a class of materials which possess both magnetic and electrical polarization with possible coupling between them. They show promise to enable new sensors and data storage devices with novel features, such as the possibility of writing polarization bits with magnetic fields at low power. The coexisting magnetic and ferroelectric order parameters are usually weakly coupled, preventing practical use. The development and study of new classes of materials with large magnetoelectric couplings is of high importance. Understanding the structure of these materials is key to this effort.

As one class of these systems, the RX3(BO₃)₄ has …

Antimicrobial Materials Via Thiol-Ene Chemistry, Dahlia Amato

Dissertations

With the increasing prevalence of antimicrobial resistance, the escalation of opportunistic/pathogenic infections is a looming global crisis. To avoid the pitfalls of conventional antibiotics, this dissertation focuses on developing macromolecular solutions to develop novel antimicrobial materials based on essential oils (thymol, carvacrol, and aldehydes). It is well established that essential oil derivatives exhibit high potency towards a wide range of pathogenic microbes. The rapid photopolymerization kinetics, limited by-products, and homogeneous network formation afforded by thiol-ene photopolymerization are utilized to either encapsulate essential oil derivatives or convert them into monomers which can subsequently be incorporated into new antimicrobial materials with new …

Polymer Nanocomposites Containing High Aspect Ratio Particulates: Innovation In Co-Extruded Multilayer Barrier Films, Kevin Meyers

Dissertations

Delaminated montmorillonite (MMT) clay/ maleic anhydride grafted LLDPE nanocomposite multilayer films with alternating layers of LDPE were produced through multilayer co-extrusion. The MMT concentration within the nanocomposite layers was increased through annealing the films in the melt due to a mismatch in interdiffusion rates of the polymer layers. Analysis of the nanocomposite layers upon annealing revealed that the platelets impinged upon one another resulting in significant improvement in oxygen barrier in the multilayer system, exceeding the results of bulk nanocomposites.

Model analysis demonstrated that increasing the nanoplatelet aspect ratio or initial concentration in the filled layers would lead to even …

Functionalized Nanoporous Carbon Scaffolds For Hydrogen Storage Applications, Christopher Carr

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 LiBH₄and NaAlH₄indicate functionalizing the carbon scaffold surface with nitrogen can shift the activation energy of hydrogen desorption in excess of …

Black Silicon – Optical Properties And Applications, Sita Rajyalaxmi Marthi

Dissertations

Crystalline Silicon (c-Si) is one of the most abundant and widely used semiconductors. Si is a semiconductor with indirect bandgap. The average reflectance of Si is about 30% in the visible range of wavelengths. Standard Si solar cells are not entirely useful in the infrared spectrum region. In order to make Si useful in a wide spectral range, the surface of Si is modified to reduce the reflectance of Si. The silicon thus modified is called Black Silicon (BSi).

This dissertation describes the model based on effective medium approximation to determine the effective optical constants, refractive index and extinction coefficient …

Preparation Of Benzoxazine Monomers And Prepolymers From Continuous Reactor: Effects Of Molecular Architecture On Properties, Andrew S. Frazee

Dissertations

Despite the modularity in molecular design and high-performance properties of benzoxazine thermoset chemistries, there are two primary shortcomings of benzoxazine marketability. Firstly, multifunctional benzoxazines are unfavorable for processing as they are glassy solids at ambient temperature. Secondly, benzoxazine chemistries are commercially synthesized using batch reactors, which are energy intensive and require the use of environmentally unfavorable solvents.

The purpose of the work herein is to address these shortcomings, which include:

1.) interrelationships between molecular architectures of synthesized monofunctional benzoxazine monomers and their ambient temperature physical states (i.e. liquid or solid) using molecular dynamics simulations and experimental comparisons,

2.) continuous high-shear …

Optimization Of The Front End Of Cdte Solar Cells, Yunfei Chen

Dissertations

The front end of CdTe solar cells consists of two layers: a transparent conducting oxide (TCO) layer and a window layer. New wider band gap materials, ZnMgO are being used to replace CdS as the window layer for the purpose of removing blue loss. For ZnMgO, three important parameters, including the atomic Mg content (x), thickness (t), and doping concentration (n) can play important roles on the performance of CdTe solar cells. In this dissertation, systematic simulation, by solar cell capacitance simulator (SCAPS), and experiments are used to investigate the influences of these …

Cellulose Reinforced Thermoplastic Composites By In-Situ Ring-Opening Polymerization, Shahab Kashani Rahimi

Dissertations

Over the past two decades, the increasing concern about the negative environmental impacts of synthetic materials has led to rising interests in utilizing renewable natural resources to develop polymer materials with comparable properties and performance to their synthetic counterparts. One of the major fields of interest is polymer composites where the replacement of synthetic fibers with bio renewable natural fibers is of great potential. However, the processing difficulties, in terms of fiber dispersion and thermal stability have limited the application of cellulosic fibers to polymers with low processing temperatures which are mostly hydrophobic polymers. As a result, the true reinforcing …

Fate Of Conductive Ink Pigments During Recycling And Landfill Deposition Of Paper-Based Printed Electronics, James Edward Atkinson

Dissertations

Printed electronics (PE) are being developed as an alternative to traditional electronics, due to the more efficient use of materials and lower cost of production. The overall goal of this study was to understand how metallic pigments in conductive inks in PE are partitioned during landfill disposal and paper recycling conditions. The purpose is to assess the potential environmental impacts of PE landfilling in terms of metal leaching and to help develop new strategies for sequestering metallic ink components while paper-based PE are subjected to conventional paper recycling methods. The objective of this research is to study the fate of …

An Investigation Of The Use Of Cerium And Polyhedral Oligomeric Silsesquioxanes For The Protection Of Polymeric Epoxy Compounds In The Low Earth Orbit Environment, Jessica Miriam Piness

Dissertations

Low Earth orbit presents many hazards for composites including atomic oxygen, UV radiation, thermal cycling, micrometeoroids, and high energy protons. Atomic oxygen and vacuum ultraviolet radiation are of concern for space-bound polymeric materials as they degrade the polymers used as matrices for carbon fiber composites, which are used in satellites and space vehicles due to their high strength to weight ratios. Epoxy-amine thermosets comprise a common class of matrix due to processability and good thermal attributes. Polyhedral oligomeric silsesquioxanes (POSS) have shown the ability to reduce erosion in polyimides, polyurethanes, and other polymers when exposed to atomic oxygen. The POSS …

Formation Of Nanostructured Epoxy Networks Containing Polyhedral Oligomeric Silsesquioxane (Poss) And Silica Nanoparticles, Amit K. Sharma

Dissertations

This dissertation is focused on structure-property-processing relationship studies based on well-defined polyhedral oligomeric silsesquioxane (POSS) modified epoxy networks to present a comprehensive understanding of hybrid network behavior. In this research, a monoamine functional POSS molecule is incorporated into the epoxy monomer as pendant unit to mimic common epoxy structures and then crosslinked to form well-defined epoxy hybrid networks. The POSS cages behave as nanosized pendant unit in the epoxy matrices, while the mass fraction of POSS cages is varied and the effects on physical properties are examined with respect to changes in network architecture.

A novel continuous reactor method is …

Design And Synthesis Of Polymer Brush Surfaces With Complex Molecular Architectures And Morphologies, Wei Guo

Dissertations

The combination of surface-initiated polymerization (SIP) and postpolymerization modification (PPM) is a powerful technique for the fabrication of functional soft surfaces. Better understanding the influence of the aforementioned factors on the PPM effectiveness is valuable for fulfilling the potential of the PPM approach for the fabrication of functional soft surfaces. Specifically, by carefully balancing modification reactivity and limitation of mass transport, polymer brush with composition heterogeneity and gradient along the normal direction of the surface otherwise unattainable by methods of direct polymerization can be fabricated via the PPM approach which opens doors to new routes to polymer brush with complex …

Effect Of Chain Rigidity On Network Architecture And Deformation Behavior Of Glassy Polymer Networks, Kyler Reser Knowles

Dissertations

Processing carbon fiber composite laminates creates molecular-level strains in the thermoset matrix upon curing and cooling which can lead to failures such as geometry deformations, micro-cracking, and other issues. It is known strain creation is attributed to the significant volume and physical state changes undergone by the polymer matrix throughout the curing process, though storage and relaxation of cure-induced strains remain poorly understood. This dissertation establishes two approaches to address the issue. The first establishes testing methods to simultaneously measure key volumetric properties of a carbon fiber composite laminate and its polymer matrix. The second approach considers the rigidity of …

Polyisobutylene Telechelic Prepolymers By In Situ End-Quenching And Post-Polymerization Modifications, Bin Yang

Dissertations

This volume focuses on the development of telechelic polyisobutylene (PIB) prepolymers by combining end-capping of living carbocationic polymerization of isobutylene (IB) with suitable reactants and post-polymerization modifications. Alkylation kinetics of PIB tert-chloride with alkoxybenzenes using either TiCl₄ or AlCl₃ were investigated. Quantitative para-position end-capped products were only achieved if the alkoxybenzene/AlCl₃ molar ratio was greater than unity; while no such molar ratio is required for TiCl₄, but the alkylation rate was slower than AlCl₃ under the same conditions. Photopolymerization kinetics analysis of PIB triphenol tri(meth)acrylates with low and high M_ns, …

Development Of Low Alloy Steel By Direct Metal Laser Sintering, Elias Jelis

Dissertations

The US Department of Defense is interested in developing, understanding, and optimizing process parameters for low alloy (4340/4140 steel) for the powder bed fusion process. Low alloy steel is used in parts where high strength and toughness are required. During parameter optimization, several aspects of the process are investigated. Powder size and morphology optimization is important for manufacturability because adequate packing is required to produce full density components. Microstructure evaluation is used in order to provide insight into parameters that lead to optimal mechanical performance and recoating performance. Influence of residual stress is evaluated with this process. Large thermal stress …

Nanostructured Morphologies In Glassy Polymer Networks, Brian Greenhoe

Dissertations

The body of this work describes a novel approach for the dispersion of multi-walled carbon nanotubes in a high T_g epoxy prepolymer matrix using a twin screw high-shear continuous reactor. The method demonstrated improves on previous dispersion methods in several ways. It offers increased efficiency through excellent heat transfer, while being solvent-less, scale-able, and tailorable to drive dispersion states to judiciously chosen dispersion states. Furthermore, it was shown that dispersion state and agglomerate morphology can be directed, in several ways, through processing conditions and also by controlling the matrix viscosity profile through cure. Broadband dielectric spectroscopy, optical hot-stage microscopy, …