Polymer and Organic Materials Commons^™

Additive Manufacturing Of Carbons From Commodity Polyolefins, Paul Smith

Dissertations

Though tremendous progress has been made engineering carbon materials across length-scales from the molecular to the macroscopic, on-demand macro-structural control of carbons is still developing. Many carbon materials like graphene, carbon nanotubes, activated carbons, and carbon fibers have powder or fiber form factors. Recent research has pioneered on-demand carbon production through additive manufacturing (AM) via 1) extrusion and post-processing of highly filled carbon slurries, or 2) printing and pyrolysis of polymeric carbon precursors such as polyimides, acrylated polyethylene glycol, and phenolics. While groundbreaking, most methods face challenges with adoption due to costly/complex materials and manufacturing processes, and large dimensional changes …

Elucidating Differences In Constitutionally Isomeric Diamine- And Bisphenol-Based Polybenzoxazine Networks, Benjamin L. G. Morasch

Dissertations

This dissertation aims to expand the fundamental understanding of diamine-based benzoxazine chemistry by examining how synthesis influences the network properties of 4,4’-ddm and phenol-based (P-ddm) benzoxazine, compared to the constitutionally isomeric bisphenol-F and aniline-based (BF-a) benzoxazine. While bisphenol-based benzoxazines such as BF-a have been studied more extensively, diamine-based benzoxazines are still relatively unexplored due to the competition with the formation of 1,3,5-hexahydrotriazine intermediates and the inconsistent thermal and mechanical properties reported in the literature. These inconsistencies stem from factors including synthetic methods, curing conditions, and degradation during polymerization that have been overlooked.

To address these issues, this dissertation is organized …

Upcycling Commodity Polymers To Advanced Materials For Energy And Environmental Sustainability, Anthony Griffin-Espinoza

Dissertations

Synthetic polymers play an essential role in nearly every aspect of our lives. Extending beyond single-use packaging, polymeric material design has progressed to attain tailorable architectures granting exceptional performance across advanced applications, including carbon-fiber reinforced polymer composites for aerospace, conductive materials for soft electronics, and drug carriers for biomedicine. While highly promising, intricately designed polymers needed to achieve excellent performance often have limited processability, complex synthetic methods, and expensive precursors. Furthermore, due to a lack of recyclability, commodity polymer waste streams result in both environmental impacts and a substantial loss of economic value. This dissertation focuses on developing robust strategies …

Understanding Crystallization Behaviors Of Polyethylene-Derived Vitrimers, Sara Valdez

Dissertations

Polyolefins (POs), particularly polyethylene (PE) and polypropylene (PP), are among the most widely utilized polymers globally, valued for their low production costs and favorable mechanical properties stemming from their semicrystalline microstructure. However, their extensive use and improper disposal have raised serious environmental and human health concerns. In response, PO-derived covalent adaptable networks (CANs) have emerged, integrating dynamic chemistries to enable recyclability and sustainable end-of-life strategies. While existing literature has largely focused on novel CAN systems, structure–property relationships, and network rearrangement in relation to thermal transitions (e.g., topological freezing temperature), the influence of network formation on crystallinity and crystallization kinetics remains …

Processing-Driven Crystallization, Morphology, And Mechanics In Pekk Composites, Nicholas Ryan Enos

Dissertations

This dissertation aims to understand how thermoplastic composites can be processed at faster manufacturing rates while identifying how processing variables influence crystallization, morphology, and mechanical properties. Throughout this dissertation, the influence of nano-scale additives, carbon fibers, rapid cooling, shear, and molecular weight on polymer physics, crystallization, morphology, and mechanics is investigated.

The inclusion of carbon nanotubes and graphene nanoplatelets accelerated crystallization, increased nucleation density, reduced lamellar thickness, and shifted governing Hoffman-Lauritzen growth regimes in PEKK. Velisaris-Seferis modelling identified a surface-induced nucleation mechanism in PEKK nanocomposites, and fast scanning calorimetry allowed for the study of rapid cooling rates, helping to identify …

Understanding Structure-Property Relationships Within Polyolefin-Derived Vitrimer Systems, Mikaela Sadri

Dissertations

Polyolefins are extremely ubiquitous materials due to their satisfactory material properties, ease of synthesis, and low cost. Unfortunately, their extensive use has led to a global plastic waste mismanagement problem. As such, notable efforts have recently focused on converting these commodity polymers into vitrimers, or dynamic networks, to extend their use-life and tailor their properties. However, the fundamental polymer physics of these emerging materials, remain largely underexplored, hindering their widespread implementation. To address this challenge and enable a more sustainable future, the overarching goal of my dissertation research is to understand the fundamental structure-property relationships within complex polyolefin-derived vitrimer systems. …

Development And Characterization Of A Pro-Angiogenic Peptide Amphiphile For Deep Dermal Burn Healing Via Spray Delivery, Loria Dimartino

Honors Theses

Severe burns and other dermatological injuries are frequently accompanied by a range of comorbidities and aesthetic challenges that patients must contend with. The complexity of burn care is exacerbated by the lack of a standardized surgical protocol, as treatment strategies are tailored to individual patient factors, including overall health status, wound size and location, as well as the expertise and resources available to the surgical team. Most commonly, deep dermal burns are treated through grafting, which effectively covers the injury site, but requires the creation of a second wound on the body of approximately the same size. This produces a …

Tuning The Morphology Of Triblock Copolymers Via Homopolymer Blending, John F. Searles

Honors Theses

Morphology plays an important role in the physical properties of block copolymer (BCP) materials. Depending on the type of morphology and chemical composition of the blocks, BCPs are used in applications ranging from soft biomaterials for biomedical devices to rigid materials for ballistics protection. Due to incompatibility between comonomers and required block weight ratios to achieve targeted morphologies, it is generally necessary to use complex, time-consuming, and expensive synthetic techniques to prepare BCPs. As a result, there is increased interest in the development of new processing methods to tailor block copolymer morphology without the need for additional synthesis. The morphological …

Tailoring The Morphology Of Block Copolymers Via Solvent-Vapor Annealing, Bayleigh Madelin Loving

Honors Theses

Triblock polystyrene-polyisobutylene-polystyrene (PS-PIB-PS) copolymers have widespread applications from thermoplastic elastomers to protective coatings for ballistic applications. The incompatibility between the soft PIB and hard PS phases leads to phase separation and subsequent formation of morphological domains like lamellae and cylinders. The structures are stabilized by physical crosslinks, which can greatly improve the toughness of the triblock systems by preventing chain pullout during tensile deformation. We tailored the morphologies (achieving different morphologies with the same block copolymer) by changing the annealing conditions of the block copolymers. Solvent vapor annealing was used to selectively activate the mobility of a particular block, causing …

Influence Of Glycopolymer Structure On Amphiphilic, Hybrid, Linear Branched Block Copolymer Properties For Use In Biomedical Applications, Kevin Green

Dissertations

The focus of this dissertation is evaluating and adding fundamental knowledge regarding the structure-property relations of glycopolymers used in the design of hybrid block copolymers (HBC) that are cable of self-assembling into delivery vehicles for biomedical applications. A shift to the utilization of natural materials in the design and fabrication of drug-delivery vehicles has garnered significant attention. Understanding the effects of linear glycopolymers content and composition on the resulting HBCs properties can provide valuable insight into how these materials may be tailored for use in targeted biological applications.

The first chapter introduces current literature on the need for improvement in …

Development And Structural Origin Of Stretchable Semiconducting Polymers And Composites, Yunfei Wang

Dissertations

Stretchable semiconductors are pivotal in advancing wearable and implantable electronics, with those boasting both high stretchability and self-healing capabilities being especially significant for a myriad of wearable applications. In this dissertation, we developed an extremely soft, highly stretchable, and self-healing elastomer based on H-bonding crosslinked amide-functionalized polyisobutylene (PIB-amide). When blended with a high-performance conjugated diketopyrrolopyrrole (DPP-T) polymer, the composite exhibits unprecedented stretchability, exceptionally low elastic modulus, and an innate ability to self-heal at room temperature.

The morphology of conjugated polymer/elastomer semiconducting composites have significant impacts on electrical and mechanical properties Further investigations focused on manipulating the phase separation size in …

Poly(Thioether) Thermosets With Gated Photodegradation, Surabhi Jha

Dissertations

Photodegradable polymer networks are attractive due to the precise spatiotemporal control and large-area applicability of light. Chemical linkages that enable these polymer networks to be photo-responsive, also hinder their applicability in ambient light. Photostable and photodegradable networks have recently been reported to overcome this challenge by combining other stimuli with light for degradation. We report the design of a network that responds to a simultaneous, dual stimulus for photodegradation. We design poly(thioether acetal) networks with benzylidene acetal moieties that are known to undergo β-scission in the presence of free thiols. By blocking these free thiols with a thermally labile protecting …

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 …

The Influence Of Diamine Curing Additives On The Network Architecture Of Phthalonitrile Thermosetting Polymers, Tyler J. Richardson

Dissertations

Phthalonitrile monomers undergo diamine-promoted polymerization by a complex reaction mechanism involving two competitive cure pathways, forming two primary network architectures: linear polyisoindoline chains and branched triazine crosslinks. The influence of the diamine curing additive on the polymerization pathway, and the influence of the resulting network architectures on cured network properties, have not been adequately explored within the phthalonitrile field. Two structurally different diamine curing additives, bis[4-(3-aminophenoxy)phenyl] sulfone (mBAPS) and 1,3-phenylenebis((4-(4-aminophenoxy)phenyl)methanone) (AEK-134), were studied for the polymerization of resorcinol phenylphosphate phthalonitrile (RPPhPN), where the influence of diamine structure and concentration on the polymerization behavior, network architecture, and bulk thermal and thermomechanical …

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 …

Investigating The Effect Of Polymer Hydrogels On The Antimicrobial Properties Of Activated Carbon Through The Utilization Of Bacterial, Viral, And Parasitic Microorganisms, Zoe Gunter

Honors Theses

Activated carbon (AC) has long been utilized in biomedical applications due to its innate antimicrobial characteristics. However, little is understood about the mechanism of action that allows AC to prohibit the propagation of different pathogen species. To further ascertain these characteristics and how they affect the propagation of pathogens, procedures were designed with bacterial, viral, and parasitic agents which were utilized in conjunction with varying concentrations of polymer hydrogels to examine the antimicrobial efficacy of AC. The studies performed for this thesis were conducted employing coconut-based AC and Noveon^® AA-1 Polycarbophil USP or Carbopol^® 974P NF hydrogels which, …

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 …

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 …

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) …

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 …

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 (

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 …

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 …

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 …

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 …