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 …

Using Afm-Ir To Study Nanoscopic Phase Behavior Of Polymer Blends And Photovoltaic Bulk Heterojunctions, Nathaniel L. Prine

Dissertations

Conjugated polymers (CPs) and polymer blends harbor the potential for high-performance organic solar cells (OSCs) due to their short energy payback time, low cost, solution processability, lightweight attributes, and flexibility. However, OSCs suffer from poor thermal stability compared to their inorganic equivalents. This study explores the thermal instability of OSCs, focusing on phase separation of the photoactive layer under heat, resulting in morphology changes and degradation of power conversion efficiency (PCE). Utilizing atomic-force microscopy coupled with infrared spectroscopy (AFM-IR) and differential scanning calorimetry (DSC), we delve into thermal stability-morphology relationships to devise strategies to improve OSC blend durability under thermal …

Software Protection And Secure Authentication For Autonomous Vehicular Cloud Computing, Muhammad Hataba

Dissertations

Artificial Intelligence (AI) is changing every technology we deal with. Autonomy has been a sought-after goal in vehicles, and now more than ever we are very close to that goal. Vehicles before were dumb mechanical devices, now they are becoming smart, computerized, and connected coined as Autonomous Vehicles (AVs). Moreover, researchers found a way to make more use of these enormous capabilities and introduced Autonomous Vehicles Cloud Computing (AVCC). In these platforms, vehicles can lend their unused resources and sensory data to join AVCC.

In this dissertation, we investigate security and privacy issues in AVCC. As background, we built our …

Application Of Deep Learning For Medical Sciences And Epidemiology Data Analysis And Diagnostic Modeling, Somenath Chakraborty

Dissertations

Machine Learning and Artificial Intelligence have made significant progress concurrent with new advancements in hardware and software technologies. Deep learning methods heavily utilize parallel computing and Graphical Processing Units(GPU). It is already used in many applications ranging from image classification, object detection, segmentation, cyber security problems and others. Deep Learning is emerging as a viable choice in dealing with today’s real-time medical problems. We need new methods and technologies in the field of Medical Science and Epidemiology for detecting and diagnosing emerging threats from new viruses such as COVID-19. The use of Artificial Intelligence in these domains is becoming more …

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 …

Ensemble Data Fitting For Bathymetric Models Informed By Nominal Data, Samantha Zambo

Dissertations

Due to the difficulty and expense of collecting bathymetric data, modeling is the primary tool to produce detailed maps of the ocean floor. Current modeling practices typically utilize only one interpolator; the industry standard is splines-in-tension.

In this dissertation we introduce a new nominal-informed ensemble interpolator designed to improve modeling accuracy in regions of sparse data. The method is guided by a priori domain knowledge provided by artificially intelligent classifiers. We recast such geomorphological classifications, such as ‘seamount’ or ‘ridge’, as nominal data which we utilize as foundational shapes in an expanded ordinary least squares regression-based algorithm. To our knowledge …

Epoxy Curing: Paramount Or Trivial? A Cure Path Dependent Inquiry, Jared Bates

Dissertations

The presented research delves into epoxy network formation corroborating reactant concentration profiles and physical property development throughout cure, providing an experimental basis for burgeoning molecular dynamics and coarse-grained simulation methodologies. Herein, three primary subjects were investigated: the first two examine neat and toughened epoxide/amine network formation with respect to various cure profiles aimed at altering reaction pathways, the final chapter intends to augment traditionally utilized activation energy (E_a) methodologies.

Neat and toughened epoxide/amine slurries were monitored in-situ throughout cure via near infrared (NIR) spectroscopy and rheological techniques. Functional group conversion and moduli development were related with specific attention …

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 …

A 3d Image-Guided System To Improve Myocardial Revascularization Decision-Making For Patients With Coronary Artery Disease, Haipeng Tang

Dissertations

OBJECTIVES. Coronary artery disease (CAD) is the most common type of heart disease and kills over 360,000 people a year in the United States. Myocardial revascularization (MR) is a standard interventional treatment for patients with stable CAD. Fluoroscopy angiography is real-time anatomical imaging and routinely used to guide MR by visually estimating the percent stenosis of coronary arteries. However, a lot of patients do not benefit from the anatomical information-guided MR without functional testing. Single-photon emission computed tomography (SPECT) myocardial perfusion imaging (MPI) is a widely used functional testing for CAD evaluation but limits to the absence of anatomical information. …

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 …

Dual-Cure Benzoxazine Networks For Additive Manufacturing, Jeremy Weigand

Dissertations

The research presented addresses the design of novel materials for additive manufacturing through a dual-cure approach that combines UV initiated free-radical polymerization of an acrylic network combined with the thermally initiated ring opening polymerization of a benzoxazine network. This work is split into three primary sections: the first and second sections focus on the synthesis and characterization of networks based on dual-cure BOX monomers, while the third develops simulation tools to further investigate thermoset networks prepared via additive manufacturing. A novel 3D printing formulation based on a multifunctional benzoxazine (BOX) monomer possessing both photo and thermally polymerizable functional groups is …

The Effect Of Precursor Design And Processing On The Semi-Crystalline Morphologies Of Polyacrylonitrile-Based Carbon Fiber, Katelyn Cordell

Dissertations

Basic research to control the morphology of polyacrylonitrile (PAN)-based carbon fiber is crucial for next generation composites as it determines their mechanical properties and final use. Poor molecular design of PAN-based precursors and fiber processing causes morphological defects and mechanical limitations.^1,2 This research focused on utilizing the controlled polymerization technique, reversible addition-fragmentation chain transfer (RAFT), of novel acrylamide comonomers to afford well-defined precursors with precisely controlled molecular design. This controlled RAFT technique improved the overall precursor graphitic structure as evident by the increased extent of stabilization and reduced activation energy as compared to precursors prepared by traditional free radical …

“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 …

Chemical And Physical Modification Of Thiol-Ene And Epoxy-Amine Networks For Advanced Control Of Gas Transport And Flame Retardant Behavior, Vivek Vasagar

Dissertations

Crosslinked polymers are widely used due to its several advantages not limited to high mechanical strength combined with the easy processability. Despite of its popular usage, the fundamental understanding of polymer structure affecting the desired properties is still lacking. This PhD thesis is in two parts, the first part is devoted to the design and developing a basic understanding of structure and chemical composition dependencies of gas transport, whereas in the second part a fundamental relationship between structure to the fire-retardant properties is established.

Membrane based gas separation technique has attracted interest of selective removal of carbon dioxide gas from …

Bioinspired Glycopolymers: Models To Investigate The Effect Of Saccharide Structure And Concentration On Amyloid Beta Aggregation, Pradipta Kumar Das

Dissertations

Aggregation and subsequent deposition of amyloid-β (Aβ) peptide on neuronal cell membranes have been implicated as a cause of Alzheimer’s disease. Gangliosides in their clustered form seed and promote the Aβ aggregation process. However, the effects of the structure and the concentration of ganglioside saccharides on Aβ aggregation are not well understood. We investigated how the specific structure of saccharides (β-D-galactose and β-D-glucose) affect the aggregation pathways, kinetics, and the aggregated structures of Aβ via in vitro experiments. The effects of the local concentration of saccharides on the Aβ aggregation were also investigated.

To mimic the multivalent effect of the …

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 …

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 …

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, …