Materials Science and Engineering Commons^™

Design And Synthesis Of Dynamic Covalent Polymer Scaffolds With Controlled Architectures, Emily Annette Hoff

Dissertations

The design and synthesis of functional, controlled polymer architectures is essential to the development of new materials with precise and tailorable properties or applications. The work described in this dissertation focuses on the development of controlled polymer architectures with dynamic linkages for the design of multifunctional materials and surfaces via robust, efficient, and stimuli-responsive strategies.

In Chapter III, a post-polymerization modification strategy based on ambient temperature nucleophilic chemical deblocking of polymer scaffolds bearing N-heterocycle blocked isocyanate moieties is reported. Room temperature RAFT polymerization of three azole-N-carboxamide methacrylates, including 3,5-dimethyl pyrazole, imidazole, and 1,2,4-triazole derivatives, afforded reactive polymer scaffolds …

Application Of Inkjet Printing Technology To Flexible Batteries, Yuan Gu

Dissertations

Printing technologies have been considered as alternative methods to fabricate thin films in recent years. More and more functional devices like resistors, sensors, antennas and even energy storage devices have been fabricated by printing technologies. As a typical digital printing technology, inkjet printing has much more advantages over the traditional mechanical printing technologies such as: low cost, computer controllable shape design and precise deposition. In this investigation, application of inkjet printing is used to fabricate conductive tracks and rechargeable lithium ion batteries.

Particle free silver ink is developed to solve this problem. In this research, silver complex solution is printed …

The Recent Development Of New Pigment Binders, Jae Young Shin

Dissertations

Pigment coatings are applied onto paper and paperboard to improve their appearance and printability. For pigmented coatings, pigments and binders are the most important ingredients so their selections are critical.

Pigment binders not only perform the basic required role of binding pigment particles to each other and bonding the base sheet, but also significantly influence the rheology, coater runnability, and drying behaviors of the coating formulation and the optical, viscoelastic, and printing properties of coated paper and paperboard products.

When considering the relative amount of binders to use in a coating, one may speak about main binder, co-binder and sole-binder. …

Flexographic Printing Of Conductive Silver Inks Onto Pdms: Surface Treatment And Novel Processes For Creating Printed Electronic Devices, Michael James Joyce

Dissertations

For the continued advancement of the field of printed electronic (PE), there is a need for a better understanding of the interactions between functional inks and substrates, which is required to optimize printability, mechanical, and functional properties for the creation of more robust and efficient printed devices. This body of work aims to advance the knowledge of the material properties of poly-di-methyl-siloxane, PDMS, films, their interactions with flexo inks, and their flexographic printability. As the printing of metals (i.e., Ag & Au) is a known area of interest pertaining to PE, this work focused on the characterization and optimization of …

3d Printed Bone Supplement Materials, Azem Khalifa Yahamed

Dissertations

Three-dimensional (3D) printing is an advanced rapid technology that can be used to make human bone substitutes with exact shape and designed structures, based on models created from actual individual bone medical Digital Imaging and Communications in Medicine (DICOM) images. Biocompatible polymers have been selected for 3D printing of human bone structures. The thermoplastics were 3D printed with Fused Deposition Modeling (FDM) are Acrylate Butadiene Styrene (ABS), Polylactic Acid (PLA) and ULTEM 9085 (a polyetherimide). The polyamide PA 2200 was 3D printed using Selective Laser Sintering (SLS). Digital ABS (a crosslinked acrylic polymer) was 3D printed using PolyJet Technology. These …

Understanding Bulk Behavior Of Particulate Materials From Particle Scale Simulations, Xiaoliang Deng

Dissertations

Particulate materials play an increasingly significant role in various industries, such as pharmaceutical manufacturing, food, mining, and civil engineering. The objective of this research is to better understand bulk behaviors of particulate materials from particle scale simulations.

Packing properties of assembly of particles are investigated first, focusing on the effects of particle size, surface energy, and aspect ratio on the coordination number, porosity, and packing structures. The simulation results show that particle sizes, surface energy, and aspect ratio all influence the porosity of packing to various degrees. The heterogeneous force networks within particle assembly under external compressive loading are investigated …

Experimental And Theoretical Evaluation Of In-Depth Damage Distribution In Sawn Silicon Wafers, Srinivasamurthy Devayajanam

Dissertations

As-sawn silicon wafers have surface damage that needs to be removed before any further processing into solar cells. This damage distribution can vary with cutting parameters such as wire size, slurry particle/diamond grit size, and wire usage. To date, there is no simple way to measure the degree of damage, damage depth, and damage distribution. But, this information is needed by the wafer manufacturers as well as solar cell manufacturers.

A technique based on sequential etching of silicon wafers and minority carrier lifetime (τ_eff) measurements is used to determine damage depth. In this technique, samples are sequentially etched …

Effects Of Expected Service Life Exposures On The Functional Properties And Impact Performance Of An American Football Helmet Outer Shell Material, David E. Krzeminski

Dissertations

The purpose of this dissertation is to gain a greater scientific understanding of the changes in functional material properties and impact performance of an American football helmet outer shell material under expected service life exposures. The research goals are to (i) quantify chemical, physical, thermal, and mechanical degradation of an American football outer shell material under expected environmental conditions and (ii) develop a linear drop test impact protocol to employ expected on-field impact conditions to American football helmet components and a plaque-foam (i.e., shell-liner) surrogate. Overall, a step-wise progression of analysis was demonstrated to concurrently quantify and understand changes in …

Hybrid Aryl-Ether-Ketone And Hyperbranched Epoxy Networks, John Misasi

Dissertations

In this dissertation, relationships between chemical structures, cure kinetics and network architectures are correlated to bulk mechanical properties for novel, hybrid epoxy-amine networks. The work is split into two primary sections: the first is the synthesis and characterization of multifunctional glassy networks based on aryl-ether-ketone diamine curatives, while the second is based on the synthesis and characterization of hyperbranched epoxy polymers and their resulting networks.

Three aryl-ether-ketone (AEK) diamines of increasing molecular weights were synthesized and used to cure 4,4’-tetraglycidylether of diaminodiphenylmethane (TGDDM); the resulting networks were compared to 4,4’-diaminodiphenyl sulfone cured TGDDM. Architectural differences were created by varying cure …

Polyacrylonitrile Copolymers: Effects Of Molecular Weight, Polydispersity, Composition, And Sequencing On Thermal Ring-Closing Stabilization, Jeremy D. Moskowitz

Dissertations

Controlled polyacrylonitrile (PAN)-based carbon fiber precursors with defined molecular weights, polydispersities, compositions, and architectures have been prepared for their study on thermal ring-closing stabilization behavior. PAN and its copolymers of number average molecular weights exceeding 170,000 g/mol were successfully synthesized via low temperature reversible addition-fragmentation chain transfer (RAFT) polymerization. RAFT polymerizations of PAN-based precursors were compared to conventional free radical solution polymerizations with a focus on the effects of molecular weight and polydispersity on structural evolution and cyclization efficiency. When RAFT polymerization was extended to copolymers, it was found that RAFT copolymers achieved greater cyclization intensities and improved thermal stability …

Development Of Dual-Cure Hybrid Polybenzoxazine Thermosets, Jananee Narayanan Sivakami

Dissertations

Polybenzoxazines are potential high performance thermoset replacements for traditional phenolic resins that can undergo an autocatalytic, thermally initiated ring - opening polymerization, and possess superior processing advantages including excellent shelf-life stability, zero volatile loss and limited volumetric shrinkage. The simplistic monomer synthesis and availability of a wide variety of inexpensive starting materials allows enormous molecular design flexibility for accessing a wide range of tailorable material properties for targeted applications. Despite the fact, once fully cured, benzoxazines are difficult to handle due to their inherent brittleness, leaving a very little scope for any modifications. The motivation of this dissertation is directed …

Production And Characterization Of Composite Nano/Micro Sized Particles By Rapid Expansion Of Supercritical Solutions (Ress) Co-Precipitation, Beidi He

Dissertations

Nanoscale composites of hexahydro-1, 3, 5-trinitro-1, 3, 5-triazine (RDX) and polymer binders were produced by co-precipitation using rapid expansion of supercritical solutions (RESS). The binders used in this study are poly (vinylidene fluoride-co-hexafluoropropylene) (VDF-HFP22), polystyrene (PS) and 7-amino-4-methyl coumarin (AMC). The RDX/VDF-HFP22 and RDX/PS co-precipitated nanoparticles were characterized by Field Emission Scanning Electron Microscopy (FE-SEM) and Transmission Electron Microscopy (TEM). The average size of produced nanoparticles is ca. 100 nm. TEM analysis of RDX/PS nano-composite shows a core-shell structure with RDX as the core material and the shell consisting of the polymeric binder. X-ray Powder Diffraction (XRPD) analysis …

New Screening Methodology For Selection Of Polymeric Materials For Transdermal Drug Delivery Devices, Roberto P. Falcone

Dissertations

As medical advances extend the human lifespan, the level of chronic illnesses will increase and thus straining the needs of the health care system that, as a result, governments will need to balance expenses without upsetting national budgets.

Therefore, the selection of a precise and affordable drug delivery technology is seen as the most practical solution for governments, health care professionals, and consumers.

Transdermal drug delivery patches (TDDP) are one of the best economical technologies that are favored by pharmaceutical companies and physicians alike because it offers fewer complications when compared to other delivery technologies. TDDP provides increased efficiency, safety …

Cure Kinetics, Morphologies, And Mechanical Properties Of Thermoplastic/Mwcnt Modified Multifunctional Glassy Epoxies Prepared Via Continuous Reaction Methods, Xiaole Cheng

Dissertations

The primary goal of this dissertation is to develop a novel continuous reactor method to prepare partially cured epoxy prepolymers for aerospace prepreg applications with the aim of replacing traditional batch reactors. Compared to batch reactors, the continuous reactor is capable of solubilizing and dispersing a broad range of additives including thermoplastic tougheners, stabilizers, nanoparticles and curatives and advancing epoxy molecular weights and viscosities while reducing energy consumption.

In order to prove this concept, polyethersulfone (PES) modified 4, 4’-diaminodiphenylsulfone (44DDS)/tetraglycidyl-4, 4’-diaminodiphenylmethane (TGDDM) epoxy prepolymers were firstly prepared using both continuous reactor and batch reactor methods. Kinetic studies confirmed the chain …

Electronic, Optical, Mechanical And Thermoelectric Properties Of Graphene, Sarang Vilas Muley

Dissertations

Graphene, a two-dimensional allotrope of graphite with sp² bonded carbon atoms, is arranged in honeycomb structure. Its quasi one-dimensional form is graphene nanoribbon (GNR). Graphene related materials have been found to display excellent electronic, chemical, mechanical properties along with uniquely high thermal conductivity, electrical conductivity and high optical transparency. With excellent electrical characteristics such as high carrier transport properties, quantum Hall effect at room temperature and unusual magnetic properties, graphene has applications in optoelectronic devices.

Electronically, graphene is a zero bandgap semiconductor making it essential to tailor its structure for obtaining specific band structure. Narrow GNRs are known to …

Inkjet Printing Multifunctional Chromatic Sensors And Chromism Study, Aide Wu

Dissertations

The thermochromism and chemochromism of polydiacetylene (PDAs) and PDA/ZnO nano composites have been systematically studied by attentuated total reflection (ATR)- Fourier transform infrared (FTIR), temperature-dependent Raman, colorimetric (using optical densitometry) and differential scanning calorimetry (DSC). Reversibility of PDAs has been enhanced by the formation of chelation between the carboxylic groups on side chain of diacetylene and Zn ion. The thermochromatic transition temperature increases with the concentration of ZnO.

Thin films of polydiacetylene (PDAs) and PDA/ZnO nanocomposites have been successfully fabricated by inkjet printing both solution type and suspension type ink. Results suggest that PDA monomers are well-aligned and closely packed …

Continuous Polymer Coating Of Host Particles By Hollow Fiber-Based Crystallizers, Dengyue Chen

Dissertations

Currently, no technique is available to continuously film coat nano-sized drug particles with a polymer to produce large amounts of free-flowing coated particles. In this work, Eudragit RL 100 and Poly (D, L-lactide-co-glycolide) (PLGA) are chosen as the coating polymers; Cosmo 55 (550 nm silica particles), Aerosi l 200 (hydrophilic 12 nm silica), Aerosil R974 (hydrophobic 12 nm silica) and Griseofulvin (10 lam drug particles) are chosen as the host particles. Two novel crystal l izers are designed and fabricated to continuously coat the host particles with different polymers: solid hollow fiber cooling crystallizer (SH FCC) and porous hollow fiber …

Polymeric Nitrogen By Plasma Enhanced Chemical Vapor Deposition, El Mostafa Benchafia

Dissertations

With the urgent need for new environmentally-friendly energetic materials, the field of polymeric nitrogen, predicted to be a high energy density energetic, is now at a critical stage in its development. In spite of extensive first principles calculations regarding the existence and stability of different polymeric nitrogen structures, their successful syntheses have been rare. This dissertation describes the first detailed study of a plasma-enhanced chemical vapor deposition (PECVD) approach to the synthesis of polymeric nitrogen. PECVD provides non-equilibrium conditions known to produce high pressure-temperature phases. Molecular nitrogen mixed with hydrogen and argon is used as the gas phase precursor to …

Utilization Of Aqueous Raft Prepared Copolymers To Improve Anticancer Drug Efficacy, Andrew Christopher Holley

Dissertations

The advent of controlled radical polymerization (CRP) techniques, along with advancements in facile conjugation chemistry, now allow synthetic tailoring of precise, polymeric architectures necessary for drug/gene delivery. Reversible addition- fragmentation chain transfer (RAFT) polymerization and its aqueous counterpart (aRAFT) afford quantitative control over key synthetic parameters including block length, microstructure, and placement of structo-pendent and structo-terminal functionality for conjugation of active agents and targeting moieties. The relevance of water-soluble and amphiphilic (co)polymers synthesized by RAFT for in vitro delivery of therapeutics in biological fluids is an especially attractive feature. In many cases, polymerization, binding, conjugation, …

Printing Functional Electronic Circuits And Components, Ahmed Tausif Aijazi

Dissertations

The purpose of this study was to investigate the challenges in printing reliable multilayer flexible circuits, devices and components. Gravure was used as the primary printing process for this work, but due to some limitations of gravure, other printing methods were also investigated. At first a systematic study was done to determine the optimum parameters for the gravure printing of sub 50 micron lines. Commercially available silver nanoparticle inks were printed on a lab scale gravure printer, Accupress®. The highest resolution line that was electrically conductive was 36μm wide. The 9μm, 18μm and 27μm lines were printed but were not …

Characterization Of Neural Ion Regulation Dysfunction During Insult And Evaluation Of Micro-Opioid Receptor Activation During Simulated Ischemia In The Pre-Botzinger Complex, Kyle F. Dobiszewski

Dissertations

The health and vitality of brain tissue is dependent upon the cells' abilities to maintain ionic homeostasis across their plasma membranes. Even slight alterations in intracellular or extracellular can have a devastating effect on excitability and neural vitality. This thesis investigates several concepts related to ion flux. First, it investigates how ion flux affects characterization of brain tissue by dielectric spectroscopy and what can be done to overcome that effect. Second, it investigates how ion flux can be used to describe the state of health of the tissue. Finally, it investigates if pharmacological intervention can attenuate some of the deleterious …

New Approaches On Deinking Evaluations, Roland Gong

Dissertations

Paper recycling in the U.S. is the most successful program of environmental sustainability. Approximately two thirds of consumed paper products were recycled, according to the EPA and AF&PA. However, domestic mills only applied one third of recycled fibers into new products, which is much lower than reported in China (67%). The domestic recycle mills claimed that outdated facilities, poor recycled fiber quality and high manufacturing cost are the major issues. They also said that these recycle mills have been put in a “no-win” position, which threatens the whole recycling loop eventually. A case study about Chinese recycle mills has been …

Influence Of Sinx/Si Interface States On Si Solar Cells, Santosh Sahoo

Dissertations

Impact of the SiN_x/n⁺-Si interface on silicon solar cell performance was investigated, where SiN_x is used as a passivation layer. Significant shifts in capacitance, conductance and leakage current characteristics were observed for metal/SiN:H/n⁺-Si MOS capacitor when it was subjected to a constant voltage stress (CVS) of +10V at room temperature. The interface trap density (D_it) across the SiN:H/n⁺-Si interface increased from 6.3 x 10⁹ to 7.5 x 10⁹ cm^-2 eV^-1 after a 500-second stress whereas the n⁺/p junction diode remained unaffected by the …

Synthesis And Characterization Of Novel Boron-Based Nanostructures And Composites, Rajen B. Patel

Dissertations

A number of nanomaterials have been synthesized by using a method that has been previously utilized to make pure boron nanostructures through the addition of different reactant gases to the process. This method was pioneered by Iqbal-Liu and will be referred to as the IL method in this dissertation. The IL method successfully created boron nanowires, boron nanoflakes, and boron nanotubes. In this dissertation, by adding methane, hydrogen sulfide, and ammonia to the process, an entire family of nanomaterials is prepared. These include nanowires, nano-heterostructures, and thin nanoplatelets of a variety of elemental compositions. These materials can be integrated with …

The Effects Of Rapid Stretch Injury On Rat Neocortical Cultures, George Constandinos Magou

Dissertations

Several key biological mechanisms of traumatic injury to axons have been elucidated using in vitro stretch injury models. These models, however, are based on the experimentation of single cultures keeping productivity slow. Indeed, low yield has hindered important and well founded investigations requiring high throughput methods such as proteomic analyses. To meet this need, a multi-well high throughput injury device is engineered to accelerate and accommodate the next generation of traumatic brain injury research. This modular system stretch-injures neuronal cultures in either a 24-well culture plate format or six individual wells simultaneously. Custom software control allows the user to accurately …

Foaming Of Amorphous Drug Delivery Systems Prepared By Hot Melt Mixing And Extrusion, Graciela Terife

Dissertations

Currently there is considerable interest from both academe and pharmaceutical industry in exploring foaming processes and their products in drug delivery applications. However, there is still little knowledge of the impact of the morphology of the foamed structures on the performance of drug products in spite of some publications in this area. Therefore, the main objective of this dissertation is to gain a fundamental understanding of the correlation between foam morphology and performance of amorphous drug delivery systems, which are comprised of an Active Pharmaceutical Ingredient (API) and Polymer excipient.

The Hot Melt Extrusion (HME) process is used to compound …

Compositional And Structural Analysis Of Nitrogen Incorporated And Ion Implanted Diamond Thin Films, Elias James Garratt

Dissertations

Significant progress in area of nano-structured thin film systems has taken place in recent decades. In particular, diamond thin film systems are being widely studied for their wear resistant, optical and electronic properties. Of the various methods researchers use to modify the structure of such films, three techniques in particular are of interest due to their versatility: modification of the growth atmosphere, growth on metalized substrates, providing an interfacial layer, and modification through post-growth ion implantation. The aim of this study is to investigate the effects each has to the structure and composition of elements. Different techniques are applied in …

The Incorporation Of Electrohydrodynamics And Other Modifications Into A Dry Spinning Model To Develop A Theoretical Framework For Electrospinning, Yuki Imura

Dissertations

The objective of this research was the development of a mathematical model of the electrospinning process using dry spinning modeling principles as a basis. This model is directed at the identification of parameters which influence final fiber characteristics, e.g., solvent concentration, temperature, spin line tension, and electric field. Preliminary computer simulations were performed; however, the generated data was inconclusive and was determined to be due in part to the complexity of the modeled system and the subsequent computational difficulties encountered. Although a comprehensive computational model of the electrospinning process has not yet been demonstrated, the theoretical development that was undertaken …

Synthesis, Molecular And Solid State Structures, And Magnetic Properties Of Sandwich Lanthanide Phthalocyanines Lacking C-H Bonds, Wycliffe A. Graham

Dissertations

A new class of sandwich phthalocyanine (Pc) compounds without C-H bonds was synthesized and characterized. They are the bis[octakis(perfluoro i-C₃F₇) octakis(perfluoro)phthalocyaninato(2−)]M(III) complexes, formulated as (F₆₄Pc)₂MH, M = Tb, Dy, Lu, Y. Single molecular magnetic (SMM) behavior in the (F₆₄Pc)₂TbH and (F₆₄Pc)₂DyH complexes was confirmed through slowed relaxation response of their magnetization in an applied time varying magnetic field during alternating current (AC) magnetic testing in the range 2 - 50 K. The energy barrier to magnetic reversal, Δ = 215 cm^-1 and …

Rational Design Of Hydrogen-Free Catalytic Active Sites, Andrei Ioan Loas

Dissertations

Materials that are organic-based and exhibit oxidative catalytic activity, including free-radical pathways, while being refractory to the activated oxygen species are not known. The synthesis of several classes of such materials, their electronic and structural characterizations as well as catalytic properties are reported. Their rational molecular design and biologically inspired reactivity are based on enzymatic active sites, which are reengineered into robust metal-organic fluoroalkylated scaffolds that, for the first time, exhibit structural asymmetry and tunable π-π interactions both in solution and solid state. In these complexes, labile C-H bonds are replaced with chemically and thermally resistant C-F bonds to create …