Polymer and Organic Materials Commons^™

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 …

“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 …

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 …

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 …

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 …

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 …

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 …

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 …

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 …

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 …

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 …

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, …

Structure-Property Relationships Of Polyisobutylene-Block-Polyamide Thermoplastic Elastomers, Morgan Dunn Heskett

Master's Theses

Thermoplastic elastomers (TPEs) are a class of polymer fit for a wide variety of applications due to their customizability. In the synthesis of these types of materials, an elastically-performing polymer, deemed the “soft block,” is combined with a stiffer “hard block” polymer, each of which can be selected based on their own specific properties in order to achieve desired material behavior in the final copolymer. Recently, the use of polyisobutylene as a soft block in combination with a polyamide hard block has been investigated for use in TPE synthesis. While the material showed some promising behavior, many properties were still …

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, …

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 …

Correlation Of Polymer Performance And Hansen Solubility Parameters, Daniel Jobse Mania

Master's Theses

Ready-to-use (RTU) grout is becoming more important to the finish and remodeling construction industry. Market research shows it is a fast-growing product that not only is creating its own space, but is beginning to supplant existing technology.

The original intent of this research was to investigate formulation parameters and how they affect grout performance. It was learned that particle size and oil absorption (OA) value are important filler properties that affect performance as much as adequate packing density and optimal pigment volume concentration (PVC) without going beyond critical PVC (CPVC).

Polymer architecture was also determined to be extremely important, but …

The Effect Of Cure Rate On Glassy Polymer Networks, Kristen M. Van De Voorde

Honors Theses

The formation of glassy polymer networks such as epoxy-amine systems may be altered by varying the temperature ramp rate that is used to cure the system. As a result, the physical and mechanical properties of the network may be changed. This work synthesized the epoxy resins diglycidyl ether of bisphenol A (DGEBA) with the amine curing agent 4,4-diaminodiphenyl sulfone (4,4’-DDS) from 35°C to 180°C using varying temperature ramp rates. Mechanical and structural properties of these samples were then analyzed to determine the effect the different temperature ramp rates had on the formation and properties of the thermoset matrix. These aspects …

Synthesis Of Acceptors For Use In Donor-Acceptor Copolymers And Characterization Of These Polymers, William D. Walker

Honors Theses

In this thesis, a selenium-derivatized acceptor was synthesized to examine the heavy atom effects of selenium on the position of the frontier molecular orbitals (HOMO/LUMO band gap) as opposed to sulfur in a donor-acceptor copolymer for use in light harvesting and detection applications. Over the course of this research, standard operating protocols for ultraviolet-visible (UV-Vis-NIR) and Fourier transform infrared (FT-IR) spectroscopies, as well as cyclic voltammetry (CV) characterization techniques were established. Once synthesized, the polymers were characterized through use of the established characterization protocols. The selenium-derivatized polymer exhibited a bathochromic shift compared to the sulfur analogue, with a solid-state absorption …

A Platform For Fast Detection Of Let-7 Micro Rna Using Polyaniline Fluorescence And Image Analysis Techniques, Partha P. Sengupta

Master's Theses

The project describes a new strategy for transducing hybridization events through modulating intrinsic properties of the electroconductive polymer polyaniline (PANI). When DNA based probes electrostatically interact with PANI, its fluorescence properties are increased, a phenomenon that can be enhanced by UV irradiation. Hybridization of target nucleic acids results in dissociation of probes causing PANI fluorescence to return to basal levels. By monitoring restoration of base PANI fluorescence as little as 10^-11 M (10 pM) of target oligonucleotides could be detected within 15 minutes of hybridization. Detection of complementary oligos was specific, with introduction of a single mismatch failing to …

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 …

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 …

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 …

Morphology-Property Relationship For Binary Organic Thin Films, Alyssa Lynn Griffin

Master's Theses

Organic thin films can be readily mass-produced through solution-based fabrication methods including ink-printing and solution-casting because their light weight, flexibility, and inexpensive sources. Their applications range from organic field-effect transistors (OFET), organic solar cells (OSC), to organic light emitting diodes (OLEDs). Compared with pure component films, binary organic thin films (BOTF) allows for novel characteristics and specialized features to handle more demanding tasks. Due to the complex intermolecular interactions in BOTF, various microscopic phases with different morphological and electronic properties may be formed and this information is difficult to extract through conventional bulk measurements.

Organic thin films can be readily …

Material Coefficient Of Thermal Expansion Investigation For Use In Additive Manufacturing Fused Deposition Modeling For Composite Tooling, Daniel Joseph Miller

Master's Theses

Polymer matrix composites are being used to manufacture light weight, high stiffness aircraft structures. These structures are often manufactured from carbon fiber reinforced epoxy. When these structures are damaged, they must be repaired to restore strength to the component to avoid the cost and logistics of having replacements parts. Occasionally, these repairs require tooling in order to make a quality repair, however, tooling generally has a long lead time. Additive manufacturing could be used to manufacture rapid tooling to create tooling for composite repairs. The issue is that polymer printed tooling has a much higher coefficient of thermal expansion (CTE) …