Engineering Commons^™

Thermally Rearranging Polyimide Networks For High-Temperature Applications, William Guzman

Dissertations

High-performance polymers can retain functional properties when exposed to long-term or short-term durations of harsh conditions, such as mechanical action, at elevated temperatures (>177 °C). A mixture of intramolecular and intermolecular forces of and between polymer chains provide excellent property retention at elevated temperatures. Specifically, the highly aromatic nature of high-performance polymer backbones provides outstanding thermal stability, which is typically attributed to π-π stacking. However, the interrelationship between thermal stability and high aromaticity creates a challenging structure-processing relationship paradigm, which causes poor polymer processability in most high-performance polymers. Herein, it was demonstrated that rationally designing a crosslinking phenylethynyl imide …

Receptor-Doped Organic Transistors: Transducing Anion Binding From Mixed Ionic-Electronic Transport, Anthony Benasco

Dissertations

Organic semiconductors based on π-conjugated polymers show remarkable properties such as high tolerance to structural defects, low processing temperature requirements, biocompatibility, ease of fabrication, and tunable properties. Conjugated polymers integrated into device arrays can exhibit collective properties sensitive to minor perturbations in the surrounding media. However, these devices rely on serendipitous sensitivity to the analyte of interest, and strategies for specific detection remain a considerable change. There remains a compelling, global need for technologies to monitor phosphate due to its prevalence in agricultural runoff, leading to fish kills and economic decline for commercial and recreational fisheries. The strong hydration energies …

Copolymer Microphase Separation, Properties, And Applications, Daniel Weller

Dissertations

Copolymers represent a broad, but critically important class of materials. Often having properties superior to either of its constituents, copolymers are used in virtually all industries including automotive, aerospace, coatings, packaging, and cosmetics. Certain copolymers microphase separate to form nanosized domains that improve the physical properties of the copolymer. The polymer community already has a thorough understanding of how phase separation occurs, but the commercialization of phase separating copolymers lags significantly behind academia. Many of the copolymers that exist that have been undercharacterized and underutilized. This dissertation examines two such polymers. The first, a hard polystyrene material with soft nanodomains. …

Thermomechanics Of Semiconducting Polymers And Their Morphological Phenomena, Luke Galuska

Dissertations

In contrast to conventional silicon-based electronics, semiconducting polymers show great promise for emerging applications in soft, flexible, and ductile electronic technologies. This is due to their polymeric nature, tailorable structure, and sub-100 nm device thickness. Despite this mechanical novelty, there remains a poor understanding of their structure-property-processing relationships, which has hindered growth within the field. This dissertation elucidates these relationships through investigation of their thermomechanics, and morphological phenomena. This was accomplished through the following projects:

1) To demonstrate the impact of backbone rigidity on semiconducting polymer thermomechanics, we varied the backbone rigidity of an NDI-based polymer by inserting flexible methylene …

Rheological Properties Of Recyclable Polymer Matrices For Advanced Composite Applications, Rahul Shankar

Dissertations

This dissertation focuses on evaluating the rheological characteristics of a variety of recyclable polymer matrices, which can compete with thermosets in a wide range of specialized applications. Studying the fundamental solid and melt-state viscoelastic properties and establishing structure-property-processing relationships is critical for the widespread adoption of these novel recyclable polymers in commercial applications. The first chapter provides an introductory overview of the different recyclable polymer matrices and their applications including high performance thermoplastics as thermoset replacements in high energy composite manufacture, multifunctional specialty thermoplastics for additive manufacturing and next generation, reprocessable covalent adaptable networks for self-healing applications. Furthermore, the important …

Atomic Oxygen Resistant Low Earth Orbit Stable Polymer Matrix Composites Employing Phenylphosphine Oxide Epoxy-Amines, Witold Fuchs

Dissertations

Atomic oxygen (AO) attacks polymer matrix composites (PMC’s) on the surfaces of spacecraft in low earth orbit (LEO) and threatens safe spacecraft operation and service life. Incorporating phenylphosphine oxide (PPO) groups into polymer chains offers a self-regenerating method of protection from AO but remains poorly understood. Herein, epoxies containing PPO groups were synthesized with increasing concentrations of phosphorus [P] from 0 to 8 wt % to investigate their AO resistance. Measurements confirmed the exposure of these materials to AO produces a passivation phosphate (POx) layer on the surface of the sample and the efficacy of the resultant layer was directly …

Practical Adhesion Measurements In Organic Coatings; Advancing Understanding And Mechanical Methods Development, Diana Gottschalk

Dissertations

“Adhesion” can be considered either a mechanical or chemical phenomenon. The mechanical interpretation describes the difficulty of separating surfaces and is useful for quantifying performance within applications that depend on bulk and interfacial properties. Chemical adhesion describes interfacial resistance to chemical attack and does not depend on bulk properties. Predicting chemical failure through mechanical measurement is confounded by the influence of bulk properties. However, the prospect is attractive because of the robust tolerance for sample geometries, allowing experiments to resemble an end-use system. The present work's primary goal was to elevate mechanical methods to provide a detailed interfacial characterization of …

Bulk Properties Correlated To The Hydrogen Bond Organization In Dendrimers, Hyperbranched Polymers, And Linear Polymers, Beibei Chen

Dissertations

Although a lot of research was conducted on dendritic polymers, our understanding of their structure-property is still limited. Our previous study, which focused on a family of dendritic polymers based on 2,2-bis(hydroxymethyl) propionic acid (bis-MPA) as a monomer, discovered unique hydrogen bond organizations contributed by their dendritic structures. However, the influence of the H-bond organization on bulk properties has yet to be understood. The goal of this dissertation is to elucidate the correlation between the H-bond organization with the dielectric and volumetric properties of bis-MPA based dendritic polymers, with an emphasis on developing a fundamental understanding of to what extent …

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) …

“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 …

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 …

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 …

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 …

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 …

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 …

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 …

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, …

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 …

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 …

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, …

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 …

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 …

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 …

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, …