Physical Sciences and Mathematics Commons^™

Synthesis Of Block Copolymer Additives For Examining Phase Morphology And Improving Mechanical Properties Of Thermoplastics Elastomers., Bishal Upadhyay

Masters Theses

Polystyrene-block-poly(1,4-butaidene)-block-polystyrene (PS-PB-PS) triblock copolymers are one of the most widely studied thermoplastic elastomers (TPEs) due to their ease of synthesis, non-polar nature, and commercial applicability. Like many block copolymers, incompatibility between PS and PB causes these TPEs to undergo microphase segregation. Many studies have examined the mechanical properties of blends of TPEs and PS homopolymer additives. However, there have been few studies focused on understanding the morphology and mechanical properties of blends of TPEs and copolymer additives with different architectures. Herein, I describe the synthesis of linear and graft copolymer additives based on the random copolymers poly(methyl methacrylate-random-cyclohexyl methacrylate) (PrC). …

The Influence Of Ion-Ion Correlations On Conductivity In Concentrated Ionic Systems, Md Dipu Ahmed

Masters Theses

This study delves into the fascinating realm of concentrated ionic systems, such as ionic liquids, superionic materials, organic ionic plastic crystals, and polyelectrolytes, which hold immense potential for energy storage applications. The focus is on understanding the intricate role of ionic correlations in shaping their ionic conductivity behavior. These correlations can either boost or impede conductivity, yet their underlying mechanisms remain elusive. Through extensive investigation of various materials, including ionic liquids with differing anionic masses, pure organic ionic plastic crystals, and doped systems, this research employs advanced techniques like dielectric spectroscopy and innovative momentum conservation models to quantify these correlations. …

Machine Learning Modeling Of Polymer Coating Formulations: Benchmark Of Feature Representation Schemes, Nelson I. Evbarunegbe

Masters Theses

Polymer coatings offer a wide range of benefits across various industries, playing a crucial role in product protection and extension of shelf life. However, formulating them can be a non-trivial task given the multitude of variables and factors involved in the production process, rendering it a complex, high-dimensional problem. To tackle this problem, machine learning (ML) has emerged as a promising tool, showing considerable potential in enhancing various polymer and chemistry-based applications, particularly those dealing with high dimensional complexities.

Our research aims to develop a physics-guided ML approach to facilitate the formulations of polymer coatings. As the first step, this …

Redox-Active Polymerization Catalysts And Their Applications, Nicholas M. Shawver

Masters Theses

Traditional catalyst systems are reliable means to produce polymers with well-defined architectures and thermomechanical properties; however, they are often limited by a narrow monomer scope and their ability access few, if any, advanced polymer architectures. To address this limitation, a new class of catalysts have recently emerged that feature redox-active moieties that may access advanced architectures through catalyst electronic modulation that arises from redox events occurring on the ligand scaffold or at the active metal center itself. For example, researchers have explored the ability of redox-active catalysts to impart “on-off” kinetic control during ring-opening polymerizations and their ability to access …

Understanding The Polymerization Of Ethyl Cyanoacrylate In The Superglue Fuming Of Latent Prints To Optimize Print Retrieval, Leondra Shawntae Lawson

Masters Theses

The cyanoacrylate fuming method (CFM) is a widespread process used in forensics to make latent prints visible for detection, acquisition, and analysis. CFM is governed by the reaction of ethyl cyanoacrylate (ECA) with biological components in fingerprints, which serve as initiators for this anionic polymerization. CFM is not a well-controlled polymerization and there are different outcomes that may result from lower temperature, one of which fits the generalization of creating more ion-pair initiators. Another effect could be minimizing termination through suppressing side reactions. Alternatively, when paired with humidity, lower temperatures may cause surface condensation, decreasing the quality of the print. …

Designing Polymer Materials For Improved Additive Manufacturing, Kaizhong Guan

Masters Theses

Currently, two of the most used additive manufacturing methods for polymers are selective laser sintering (SLS) and fused filament fabrication (FFF). Although at high market size, they both have imperfections. The materials for SLS are limited and the objects manufactured by FFF existing anisotropic behavior. Targeting on these drawbacks, this thesis has proposed a novel method to prepare polypropylene (PP) microsphere which is suitable for SLS with low cost and scalable potential; and a novel material with polycarbonate as matrix that has shown a decrease in anisotropy after FFF printing.

The PP microsphere in this thesis was prepared via liquid-liquid …

Synthesis Of Well-Defined Binary Mixed Brushes On 20 Nm Silica Nanoparticles And Asymmetrically End- Functionalized Semicrystalline Poly(Ε-Caprolactone)S, Andrew J. Chancellor

Masters Theses

Well-defined polymers and polymer brushes play an important role in the understanding of their behavior under various conditions and in the fabrication of nanostructured functional materials. This Master’s thesis work focuses the synthesis of two well-defined systems: binary mixed homopolymer brushes grafted on 20 nm silica nanoparticles (NPs) for understanding their microphase separation behavior and asymmetrically end-functionalized semicrystalline poly(- caprolactone) polymers for use in the fabrication of multicomponent polymer brushes on flat substrates with various architectures. While theoretical and simulation studies have revealed intriguing morphologies of mixed homopolymer brushes grafted on nanospheres with a size similar to those of grafted …

Synthesis And Evaluation Of Acetylcholine Molecularly Imprinted Polymers, Nathaniel Donald Thiemann

Masters Theses

Polymers imprinted with acetylcholine during synthesis were prepared in order to evaluate their potential for implementation as a novel recognition element in acetylcholine biosensors. Biosensors, such as the glucose monitor, are used to rapidly detect and quantify a target analyte. Acetylcholine biosensors have already been produced using enzymatic recognition elements, but they are currently expensive and plagued by short viability. Molecularly imprinted polymers are not only cheap and durable, but have also been successfully used as a recognition element in biosensors for other analytes. Therefore, computational tools were used to rationally design acetylcholine molecularly imprinted polymers. Three chemicals, itaconic acid, …

The Effect Of Plant Source On Lignin-Based Polyurethanes And The Interdiffusion Dynamics Of Semi-Rigid Polymers, Jason Michael Lang

Masters Theses

The work reported in this thesis increases our understanding of the effect of lignin plant source on the mechanical and morphological properties of lignin-based polyurethanes and the interdiffusion of glassy/liquid bilayer thin films. The interdiffusion of glassy/liquid polymer pairs has received much less attention than liquid/liquid bilayers, leading to conflicting results and unresolved discrepancies. Therefore, the reported study of interdiffusion between polysulfone glassy/liquid polymer layers provides insight into the dynamics of these systems.

This thesis first reports the correlation between the mechanical properties of lignin-based polyurethanes and the lignin plant source. Lignin is a molecule that can be used as …

Influence Of Biomimetic Chelating Packaging On Natural Antimicrobial Efficacy, Paul Castrale

Masters Theses

The iron chelating molecule, ethylenediaminetetraacetic acid (EDTA) is used in food applications for the preservation of oxidation prone ingredients. Research has suggested that EDTA is also capable of enhancing the antimicrobial effectiveness of various compounds including naturally-derived antimicrobials. With consumer demand for cleaner food labels, there remains an opportunity to introduce new chelating technology to replace synthetically-derived EDTA. Through photographting and chemical conversion, hydroxamic acid ligands were covalently bound to polypropylene films resulting in polypropylene-graft-poly(hydroxamic acid) (PP-g-PHA). The resulting films demonstrated an ability to chelate 64 nmol/cm² from an iron saturated environment or 163 nmol/cm …

Incorporating Carbon Nanotubes Into Carbon Fiber Via Surface Modification, Robert Benjamin Ripy

Masters Theses

Ever more advanced materials need to be designed to further the exploration of avenues of science and engineering. Metals and traditional composites are not meeting the needs of today’s stringent demands for lightweight and strong materials. There is a need for advanced materials that are lighter and stronger to replace conventional materials; carbon fiber composites became the obvious choice because of their outstanding mechanical properties. Polyacrylonitrile (PAN) based carbon fiber has reached its apex in terms of its strength to weight ratio. Carbon nanotubes (CNTs) offer a lightweight and potentially stronger alternative to PAN based fibers. However, it is difficult …

Siloxane And Silane-Functionalized Polynorbornenes As Membranes For Passive Carbon Dioxide Separation, Eunice Koheun Hong

Masters Theses

In 2012, carbon dioxide (CO₂) [carbon dioxide] accounted for approximately 82% [percent] of all U.S greenhouse gas emissions.¹ These excessive CO2 levels have been attributed to climate changes that have a range of negative effects on human health and welfare.1 In an effort to decrease these emissions, polymeric membranes consisting of silane- and siloxane-functionalized norbornene units have been targeted as a potential solution for the passive separation of CO2 from other non-greenhouse gases. These substituted norbornene-based polymers were synthesized via vinyl-addition polymerization. Through a series of catalyst trials, commercially available palladium and nickel catalysts were compared along …

Preparation And Characterization Of Thermodynamically Controlled Polymer Nanocomposites, Jiadi Hou

Masters Theses

The mechanical and physical properties of polymeric materials can be greatly improved by adding nanoscale additives. To mediate the dispersion of nanoparticles in polymers, it is often necessary to modify their surfaces to prevent aggregation. While polymer nanocomposites system consisting of homopolymer-grafted nanoparticles are well understood, copolymer-functionalized nanoparticles are less well understood but provide additional ways to alter dispersion through the use of chemically different comonomers. In this thesis, polystyrene nanocomposites blended with copolymer-grafted nanoparticles were prepared and studied. The particular comonomers used were methyl methacrylate and cyclohexyl methacrylate, which provides miscibility with polystyrene. Polymers with varying comonomer ratios were …

Molecular Interpretation Of A Trigger For Controlling An Amine Isocyanate Polyurethane Reaction, Katherine V. Carrasquillo

Masters Theses

The temperature profile needed to complete the reaction between the sodium-diamine complex and the isocyanate terminated prepolymer has been established. The sodium diamine complex has the advantage of blocking the nearly instantaneous reaction between the diamine and isocyanate from taking place until it is released at elevated temperatures. Because of its low melting temperature (~40 °C) and its low molecular weight (low viscosity), this chain extension reaction is not dependent on the participation of the prepolymer. Instead, the rate of reaction is dependent on the dissolution of the 4,4’-methylenedianiline (MDA) complex into the system. The dissolution of the MDA complex …

Correlating Morphology To Performance In Conjugated Polymer Nanocomposite Thin Films, Siddharth Pradhan

Masters Theses

The morphology and performance of thin films that consist of conjugated polymers and nanoparticles are investigated in this thesis. In the first system, the morphology of the nanocomposite that consists of low band gap alternating copolymers with a methano-fullerene are determined by neutron scattering and correlated to their photovoltaic performance as polymer solar cells. These results show that the conjugated alternating copolymers have high miscibility relative to other conjugated polymers. The analysis of the scattering data shows that the morphology of the conjugated polymer-fullerene bulk heterojunction can be described as the formation of aggregates on two length scales. Important parameters …

Biodegradable Nano-Hybrid Polymer Composite Networks For Regulating Cellular Behavior, Charles Henley Sprague

Masters Theses

Photo-crosslinkable polymeric biomaterials have emerged in the field of biomedical research to promote tissue regeneration. For example, scaffolds that can be crosslinked and hardened in situ have been known to make suitable implant alternatives. Since injectable and photo-crosslinkable biomaterials offer the advantage of being minimally invasive, they have emerged to compete with autografts, a current highly invasive method to repair diseased tissue. A series of novel photo-crosslinkable, injectable, and biodegradable nano-hybrid polymers consisting of poly(ε-caprolactone fumarate) (PCLF) and polyhedral oligomeric silsesquioxane (POSS) has been synthesized in our laboratory via polycondensation. To engineer the material properties of the nano-hybrid networks, varied …

Characterizing The Morphology Of Solvent Annealed Pcbm/P3ht Bilayers Using Gixrd And Raman Spectroscopy, Tyler Evan Mcpherson

Masters Theses

A growing demand for new forms of renewable energy has been at the forefront of scientific research. Organic photovoltaics (OPVs) provide a promising alternative to the expensive inorganic solar cells used today. Poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl C61-butyric acid methyl ester (PCBM) are common donor and acceptor materials used in the active layer of an OPV device. These systems have reached power conversion efficiencies of approximately 12 %. However, little is known about the actual morphology. A better understanding of the morphology would allow researchers to optimize device fabrication to increase the device performance. As-cast devices are limited by the processing …

Synthesis, Characterization, And Functionalization Of 2-Vinyl-4,4-Dimethylazlactone Brushes To Create Bio-Inspired Materials, Camille Marie Kite

Masters Theses

Functional materials built from polymer scaffolds inspire many potential uses, including as biomaterial surfaces or sensors. In situ functionalization using well-defined polymer “brushes” made by tethering polymer chains to a surface by one of their ends is explored. Specifically, poly(2-vinyl-4,4-dimethylazlactone) (PVDMA) chains, which contain a reactive azlactone ring at each repeat unit, are tethered to a surface to create brushes and these films are functionalized using a variety of small molecules, primarily amines or peptides. Relationships between polymer brush thickness, size of the functionalizing molecule, solution concentration, reaction time, and extent of functionalization were determined through measurements of brush thickness …

The Impact Of Non-Covalent Interactions On The Dispersion Of Fullerenes And Graphene In Polymers, Say Lee Teh

Masters Theses

The work presented in this dissertation attempts to form an understanding of the importance of polymer connectivity and nanoparticle shape and curvature on the formation of non-covalent interactions between polymer and nanoparticles by monitoring the dispersion of nanoparticles in copolymers containing functionalities that can form non-covalent interactions with carbon nanoparticles.

The first portion of this study is to gain a fundamental understanding of the role of electron donating/withdrawing moieties on the dispersion of the fullerenes in copolymers. UV- Vis spectroscopy and x-ray diffraction were used to quantify the miscibility limit of C60 fullerene with the incorporation of electron donor-acceptor interactions …

Macroporous Polymer Synthesis And Characterization: The Role Of Molecular Recognition In The Regioselectivity Of Sucrose Reactions, Gilbert Joshua Matare

Masters Theses

Molecular recognition has recently emerged as a unique technique for making synthetic polymers with selective binding cavities which can stereoselectively and regioselectively bind to a template molecule in a fashion similar to natural enzymes and antibodies. Its industrial applications in chemistry and biomedicine have been recently exploited. Typical examples include the resolution of amino acids, enantio-separation of racemates and bioactive molecules, selective binding of metal ions and in HPLC investigations. Our research is focused on applying molecular recognition studies to improve the regioselectivity of sucrose reactions.

Sucrose is an abundant industrial raw material of immense industrial importance however, its full …

Synthesis Of Organometallic Polymers, Po-Chang Chiang

Masters Theses

By the middle of the nineteenth century, organic chemists found high molecular weight compounds as by-products of some of their experiments. These compounds were thought of as products of a failed reaction. It was not until sixty years ago that the first polymers were deliberately synthesized. Today polymers are used in almost every facet of life and they are becoming more important with each passing day.

This research project focused on synthesizing conducting organometallic polymers. By linking aromatic rings with transition metals, the resultant polymers should have good electrical conductivity because of the interaction of (a) the p electrons on …