Polymer and Organic Materials 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 …

Formulation And Optimization Of Algae-Filled Polylactic Acid Thermoplastic Compounds For Improved Biodegradation, Sydney A. Cole

Honors Theses

Conventional plastics derived from non-renewable petrochemicals – especially from fossil reserves – have become an integral part of human life because their structure can be chemically manipulated to obtain a wide range of properties and geometries necessary in nearly all industries. The volume and rate at which petroleum plastics are produced, used, and discarded has incited several significant issues related to human health, environmental conservation, and ecological biodiversity. To address these issues, many institutions have begun investigating solutions in both the development and end-oflife phases of plastic production and waste. In this thesis, a Chlorella-dominated algae mixture is dried and …

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. …

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 …

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 …

Chitosan Graphene Composite Fabrication And Characterization For Treatment Of Harmful Algal Blooms And Toxins, Sarah Zetterholm

Master's Theses

Chitosan graphene composites were fabricated and characterized as a management strategy for harmful algal blooms (HABs) caused by various species of cyanobacteria. These chitosan graphene materials were compared to previously studied chitosan graphene-oxide composites in both material properties and HAB treatment. In previous studies, adsorption of the cyanobacteria onto the surface of the composite materials has been observed. Investigations of the pure materials for these composites are also included in this study to determine whether removal is a result of charge interactions with the composite, or as an inherent property of the graphene or graphene oxide. Initial results suggest that …

Effects Of Static Mixer Geometry On Polyurethane Properties, Christian R. Dixon

Honors Theses

The field of additive manufacturing has gained significant academic interest in the past few decades with a recently developed type of three-dimensional (3D) printing. Reactive extrusion additive manufacturing combines precursor materials within a static mixer (SM) head, where polymerization begins before deposition. Variable static mixer geometries currently exist, but the relationship between mixer geometry and post-polymerization mechanical properties is undefined. To elucidate this relationship, a series of experiments with identical chemistry was performed using a high shear SM, a low shear SM, and a comparative batch reaction. While higher shear mixing trends with faster polymerization for step-growth polymerizations, consistent precursor …

Utilizing The Oxygen-Barrier Properties Of Poly(Isobutylene) To Enhance Photon Upconversion In Thermoplastic Elastomers, Haley Carroll

Honors Theses

Upconversion (UC) is the conversion of low energy light to higher energy light. It is utilized for a broad range of applications such as solar energy harvesting, microscopy of cellular biology, and cancer therapy. Specifically, triplet-triplet annihilation UC (TTA-UC) involves two dye species, a sensitizer and an annihilator, which are capable of upconverting noncoherent light such as sunlight. Traditionally, TTA-UC is achieved in solution, rubbers, or glasses, however, this work probes the capabilities of a thermoplastic elastomer (TPE) matrix to examine the effect of phase-separated morphology on the energy transfers necessary for TTA-UC. The system herein consists of poly(styrene-isobutylene-styrene) (SIBstar) …

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 …

Tacky Elastomers To Enable Tear-Resistant And Autonomous Self-Healing Semiconductor Composites, Song Zhang, Yu-Hsuan Cheng, Luke Galuska, Anirban Roy, Matthias Lorenz, Beibei Chen, Shaochuan Luo, Yen-Ting Li, Chih-Chien Hung, Zhiyuan Qian, Peter Blake Joseph St. Onge, Gage T. Mason, Lewis Cowen, Dongshan Zhou, Sergei I. Nazarenko, Robson F. Storey, Bob C. Schroeder, Simon Rondeau-Gagné, Yu-Cheng Chiu, Xiaodan Gu

Faculty Publications

Mechanical failure of π-conjugated polymer thin films is unavoidable under cyclic loading conditions, due to intrinsic defects and poor resistance to crack propagation. Here, the first tear-resistant and room-temperature self-healable semiconducting composite is presented, consisting of conjugated polymers and butyl rubber elastomers. This new composite displays both a record-low elastic modulus (

Selfsame Epoxide-Amine Microparticle Systems: Investigation Of Crosslink Density, John J. Peyrefitte

Honors Theses

Epoxide-amine matrix materials containing microparticles with the same chemical composition provide a model system to study interphase formation in highly crosslinked epoxide-amine matrix materials. The epoxide monomer was varied between three different monomer systems to study the model system’s relationship with crosslink density. The same amine monomer, cure procedure, and stoichiometric ratio of epoxide and amine groups were used to prepare each type of microparticle and matrix material. The differences in the epoxide monomer structure affected the crosslink density of the unmodified matrix material, which was concluded to influence the effect of microparticle presence on crosslink density. For the unmodified …

Investigation On The Morphology Of Charge-Transfer Complexes In Low Density Polyethylene, Wade Korf

Master's Theses

Fillers are used ubiquitously throughout the fields of polymer and material science to overcome many inherent limitations to polymeric materials (i.e. poor stiffness or strength) and to expand their potential applications. There is a need to develop controllable particle architectures to better understand fundamental structure-property relationships in particle reinforced polymer composites. Charge-transfer complexes (CTCs) can assemble in situ into various needle and dendritic shapes via simple fabrication processes and at low loading levels. In this study, the effect of tetrathiafulvalene (TTF) and 7,7,8,8-tetracyanoquinodimethane (TCNQ) CTC crystallites of various shapes and sizes on composite mechanical properties was investigated in an LDPE …

Thiol-Induced Degradation Of Hydrogels Utilizing Multiresponsive Dithiomaleimides Crosslinkers, Kundu Thapa

Honors Theses

Hydrogels are hydrophilic, three-dimensional materials used as platforms for various biomedical applications such as drug delivery, biosensors, or as scaffolds in tissue engineering. The ability to degrade on demand in response to biological cues is particularly attractive whether dealing with microgels or if one aims to release an active ingredient from a scaffolding material. For instance, many cancer-remediation drug delivery platforms leverage the high concentration of glutathione, a thiol-containing tripeptide, found in cancerous cells. In this work, poly(ethylene glycol) acrylate hydrogels were fabricated using dithiomaleimide (DTM) moieties. DTMs are known to undergo thiol-exchange reactions favoring the dissolution of the hydrogel …

Tailoring Photodegradation Rates Of Acetal-Containing Polymer Networks, Michael Sandoz

Honors Theses

In this thesis, we explore the degradation of poly (thioether acetal) thermosets via a photoinduced thiol-catalyzed ß-scission of acetal linkages incorporated as network crosslink junctions. Specifically, a library of bis-allyl acetal-containing monomers derived from para-substituted benzaldehydes was synthesized and formulated into photopolymerizable thiol-ene resins with commercially available thiol monomers. By varying the electron donating or withdrawing nature of the monomer substituent, we explored the impact of substituent effects on the rate of polymer degradation. Furthermore, we compare the results to those expected from a classical Hammett-type relationship of substituent electronic effects. FTIR was employed to track the appearance of the …

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 …

Improved Data Acquisition Using A Novel Dynamic Mechanical Analysis Sample Preparation Technique: The Numbers Do Not Lie, Jordan J. Winetrout

Honors Theses

Dynamic mechanical analysis (DMA) is a technique commonly used to identify the thermomechanical properties of polymeric materials. In the aerospace industry, a typical DMA sample is a glassy epoxy-amine polymer network. On a laboratory scale, these types of materials are cured in a silicon mold and sanded by hand to yield a sample with testable dimensions. This preparation technique is time consuming and causes sample imperfections which negatively affects data acquisition. This thesis aims to absolve the issues with DMA sample preparation by using a custom vacuum housing and a DeWALT^TM brand orbital sander. This novel approach has been …

Design Process Of A Novel Dynamic Mechanical Analysis Sample Preparation Methodology, Julian M. Richardson

Honors Theses

The technique of dynamic mechanical analysis (DMA) has been a frontrunner in the field of polymer science for decades. It’s used as a tool for characterization has been integral in mankind’s understanding of the properties of polymeric materials. The procedure for obtaining data using DMA is widespread and standardized, however the procedure for preparing the samples is a list of dimensions and tolerances with no mention of how to obtain said dimensions. Every research group using DMA is left to their own devices to prepare samples. This discontinuity can create the problem of nonuniform results across the scientific community. This …

“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 …

Corner Sealants For Tactical Shelters, Janine Carlita Nowak

Honors Theses

The demand for a lightweight, easy-assembly tactical shelter is high for those faced with unexpected disasters and global conflicts. This project focuses on designing and prototyping the corner sealant for such a shelter. Two materials were chosen and tested: an in-house thermoplastic polyurethane (TPU) and Texin 950. Thermogravimetric Analysis (TGA) was performed on both of these materials. The in-house TPU showed initial degradation at 282.50 °C and sample degradation at 457.45 °C. Similarly, Texin 950 showed initial degradation at 293.68 °C and sample degradation at 453.26 °C. Differential Scanning Calorimetry (DSC) was then run. The crystallization temperature (Tc) was observed …

Characterization And Selection Of Hydroxyl-Terminated Polybutadiene Polymers For High-Strain Applications, Nathaniel Prine

Honors Theses

Understanding the behavior of hydroxyl-terminated polybutadiene (HTPB) as a composite matrix is imperative for the development of future military and aerospace munition technology. As a vital component of solid rocket fuel, HTPB strongly contributes to the fatigue behavior, burn-rate, and other properties that can cause critical failure of the rocket if not formulated properly. The purpose of this research is to identify traits characteristic of poor-performing HTPB matrices by analyzing two samples labeled as either “good” or “bad” based on their performance as a fuel matrix. Samples were analyzed via 1H NMR and GPC to determine their epoxy content, hydroxyl …

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 …

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 …