Engineering Commons^™

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 …

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 …

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 …

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 …

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 …