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Articles 31 - 60 of 76
Full-Text Articles in Physical Sciences and Mathematics
Design-Structure-Property Relationships Of Purine-Based Copolymers And Chromophores, Graham Smith Collier
Design-Structure-Property Relationships Of Purine-Based Copolymers And Chromophores, Graham Smith Collier
Doctoral Dissertations
Understanding the relationship between monomer design and polymer properties is imperative for developing polymeric systems that can find applicability in targeted technologies. Purines have been extensively studied across many scientific disciplines and are useful due to the diverse properties they possess, which is due in part to the broad scope of precise synthetic transformations that are used to tailor their properties. The overarching goal of my dissertation involves developing the synthesis of “poly(purine)s” and investigating the effect of purine monomer design on polymer properties. In this vein, poly(purine)s and purine-based donor-acceptor small-molecules are synthesized via Stille cross-coupling reactions with a …
Thermally Robust And Redox Active Catalysts: Studying Their Behavior For Ethylene And L-Lactide Polymerization, Lauren Ashley Brown
Thermally Robust And Redox Active Catalysts: Studying Their Behavior For Ethylene And L-Lactide Polymerization, Lauren Ashley Brown
Doctoral Dissertations
The development of homogenous single-site catalysts has significantly impacted the field of organometallic chemistry. The well-defined structures of homogenous catalysts make it less cumbersome to understand and develop methods to tailor these compounds for specific catalytic processes. Currently, polymerization catalysis is a major division in organometallic chemistry due to the global demand for polymeric materials such as polyethylene (PE) and polypropylene (PP), based on their low-cost feedstock, remarkable mechanical properties, and their use in a wide range of applications. However, bioplastics have become a highly sought-after alternative to conventional petrochemical-based plastics due to their biodegradability and derivatization from renewable resources. …
Hetero-Atom Containing Functional Polymers: Synthesis, Characterization And Applications, Hongbo Feng
Hetero-Atom Containing Functional Polymers: Synthesis, Characterization And Applications, Hongbo Feng
Doctoral Dissertations
A mission to manage ever increased energy demands and reduce carbon foot print has challenged scientists and engineers to develop new materials with superior characteristics. In this scenario, lithium-ion batteries have been the dominating technology for not only applications in consumer electronics but also are essential for clean energy storage. On the other hand, the capture and separation of CO2 [carbon dioxide] in power generation and in industrial processes is considered to be a key to reduce the carbon footprint.
Living anionic polymerization along with controlled polymerization techniques has realized the preparation of a wide variety of functional polymers …
Development Of High Performance Gas Separation Membranes Through Intelligent Catalyst And Monomer Design, Kevin Richard Gmernicki
Development Of High Performance Gas Separation Membranes Through Intelligent Catalyst And Monomer Design, Kevin Richard Gmernicki
Doctoral Dissertations
Polymer membranes are a valuable tool for separating components of liquid and gas mixtures. Heavily inspired by biological systems, the idea of using the intrinsic properties of polymers to perform otherwise energy-intensive tasks is attractive for applications such as water desalination, natural gas sweetening, and post-combustion carbon capture. Of particular interest to our research group, post-combustion carbon capture is a promising potential solution aimed at reducing the carbon footprint involved with production, transportation, and storage of electrical energy generation.
Every year, the United States produces close to seven billion metric tons of carbon dioxide, of which a significant portion is …
Impact Of Macromolecular Design On Self-Assembly Properties Of Block Copolymers: Effect Of Tunable Chain Flexibility And Chain Topology, Kamlesh Ramesh Bornani
Impact Of Macromolecular Design On Self-Assembly Properties Of Block Copolymers: Effect Of Tunable Chain Flexibility And Chain Topology, Kamlesh Ramesh Bornani
Doctoral Dissertations
The generation of well-ordered complex structures from constituent block copolymeric building blocks by the spontaneous process of self-assembly is useful in various technologies. The well-defined 3D structures are dictated by complex energetic interplays and their shape is controllable by both preparative conditions and macromolecular design. This dissertation work aims at exploring the effect of chain flexibility and chain topology design changes on phase behavior of block copolymers in solution. Further, we exploit the tunable flexibility of the semiflexible polymers in studying dispersion and controlling macroscale thermal properties in polymer nanocomposites.
The experimental design is based on two model systems: The …
All Acrylic Based Thermoplastic Elastomers: Design And Synthesis For Improved Mechanical Performance, Wei Lu
All Acrylic Based Thermoplastic Elastomers: Design And Synthesis For Improved Mechanical Performance, Wei Lu
Doctoral Dissertations
Thermoplastic elastomers (TPEs) have been widely studied because of their recyclability, good processability, low production cost and distinct performance. Compared to the widely-used styrenic TPEs, acrylate based TPEs have potential advantages including exceptional chemical, heat, oxygen and UV resistance, optical transparence, and oil resistance. However, their high entanglement molecular weight lead to “disappointing” mechanical performance as compared to styrenic TPEs. The work described in this dissertation is aimed at employing various approaches to develop the all acrylic based thermoplastic elastomers with improved mechanical performance.
The first part of this work focuses on the introduction of acrylic polymers with high glass …
Effect Of Molecular Structure Of Side Chain Polymers On "Click" Synthesis Of Thermosensitive Molecular Brushes, Christie Maggie Lau
Effect Of Molecular Structure Of Side Chain Polymers On "Click" Synthesis Of Thermosensitive Molecular Brushes, Christie Maggie Lau
Chancellor’s Honors Program Projects
No abstract provided.
The Effect Of Illumination On The Conformation And Thermodynamics Of Conjugated Polymers, Brian Frank Morgan
The Effect Of Illumination On The Conformation And Thermodynamics Of Conjugated Polymers, Brian Frank Morgan
Doctoral Dissertations
This dissertation explores the effects which illumination has on the structure and conformation of conjugated polymers, both in solution and the bulk. Conjugated polymers are an important class of optoelectronic polymeric materials which make up the active layer of key organic electronic devices such as organic photovoltaics, transistors, and light emitting diodes. Considering the strong link between polymer chain structure and device efficiency in these materials, a comprehensive understanding of certain experimental conditions which may influence this conformation and thusly alter the functionality of the devices predicated upon them is of vital importance.
The first part of this dissertation provides …
Synthesis And Behavior Of Stimuli-Responsive Shape-Changing Linear Molecular Bottlebrushes, Daniel Mark Henn
Synthesis And Behavior Of Stimuli-Responsive Shape-Changing Linear Molecular Bottlebrushes, Daniel Mark Henn
Doctoral Dissertations
Molecular bottlebrushes are composed of polymer side chains densely grafted to a macromolecular backbone. The main focus of this dissertation work is the synthesis and behavior of linear molecular brushes that can undergo unimolecular size and shape changes in response to environmental stimuli in dilute aqueous solution. Chapter 1 provides an introduction to molecular bottlebrushes and stimuli-responsive polymers.
Chapter 2 presents the development of a robust method for the synthesis of well-defined molecular brushes by a “grafting to” approach using copper-catalyzed azide-alkyne cycloaddition “click” reactions. Well-defined, new azide-containing backbone polymers with different lengths and high degrees of azide functionality were …
Synthesis And Characterization Of New Multifunctional Initiators For Anionic Polymerization And The Use Of Poly(4-Hydroxystyrene) As A Template For New Polymers, Christopher Michael Hurley
Synthesis And Characterization Of New Multifunctional Initiators For Anionic Polymerization And The Use Of Poly(4-Hydroxystyrene) As A Template For New Polymers, Christopher Michael Hurley
Doctoral Dissertations
This dissertation explores the synthesis and use of multifunctional anionic polymerization initiators for the purpose of opening the gateway to the synthesis of polymer architectures of greater complexity. First the multifunctional oxyanion initiator generated by reacting poly(4-hydroxystyrene) with sodium hydride was used to synthesize a previously unknown polymer containing an aryl halide functional group. The homopolymer solution self-assembly behavior of poly(4-hydroxystyrene) and the newly synthesized poly (4-bromo-phenyloxystyrene) were both investigated. This is followed by the synthesis and characterization of multifunctional alkyne core molecules and random copolymers of polystyrene-co-poly(4-hydroxystyrene) which served as templates for the synthesis of new random copolymers of …
Hybrid Micellar Network Hydrogels Of Thermosensitive Hydrophilic Triblock Copolymers And Thermosensitive Hairy Nanoparticles, Bin Hu
Doctoral Dissertations
Hybrid micellar network hydrogels, composed of thermosensitive hydrophilic triblock copolymers and thermosensitive polymer brush-grafted nanoparticles (hairy NPs), exhibit intriguing rheological properties. This dissertation work studies thermosensitive hybrid hydrogels with NPs positioned either inside or outside the core of block copolymer micelles.
Chapter 1 is an introduction. Chapter 2 examines the effect of NP’s location on properties of hybrid hydrogels of a thermosensitive ABA triblock copolymer and hairy NPs. Two batches of thermoresponsive polymer brush-grafted silica NPs and an ABA triblock copolymer with thermosensitive outer blocks were prepared. When the lower critical solution temperature (LCST) of hairy NPs was similar to …
Synthesis And Application Of Polymer Brush-Grafted Nanoparticles As Hydrogel Gelators And Lubricant Additives, Roger Anthony Emory Wright
Synthesis And Application Of Polymer Brush-Grafted Nanoparticles As Hydrogel Gelators And Lubricant Additives, Roger Anthony Emory Wright
Doctoral Dissertations
This dissertation describes the synthesis of polymer brush-grafted nanoparticles (hairy NPs) and an analysis of their behavior or utility in multiple areas. The hairy NPs were synthesized from silica NPs functionalized with initiating moieties by surface-initiated atom transfer radical polymerization. A brief introduction to hairy NPs, with a focus on the synthesis and behavior of stimuli-responsive polymer brush-grafted particles, is given in Chapter 1 to provide context for this work.
Chapters 2 and 3 present the synthesis of thermosensitive diblock copolymer brush-grafted nanoparticles designed as hairy NP analogues in place of thermosensitive block copolymers micelles for the construction of hybrid, …
Improving And Understanding Inter-Filament Bonding In 3d-Printed Polymers, Madeline S. Stark
Improving And Understanding Inter-Filament Bonding In 3d-Printed Polymers, Madeline S. Stark
Chancellor’s Honors Program Projects
No abstract provided.
Incorporating Carbon Nanotubes Into Carbon Fiber Via Surface Modification, Robert Benjamin Ripy
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 …
Understanding The Influence Of Non-Covalent Interactions And Nanoparticle Geometries In Carbon Based Polymer Nanocomposites, Bradley Carroll Miller
Understanding The Influence Of Non-Covalent Interactions And Nanoparticle Geometries In Carbon Based Polymer Nanocomposites, Bradley Carroll Miller
Doctoral Dissertations
Low-loading polymer nanocomposites (PNC) are an area of great interest in polymer science. As nanoparticles (NP) are typically expensive in comparison to matrix materials; the low loading regime makes the most efficient use of materials, and represents the optimum for realizing cost effective, high-performance PNCs. However, formulating effective low-loading composites is not without challenges. In addition to the typical requirement of good dispersion for efficient translation of NP properties to the bulk, low-loading composites can sometimes exhibit anomalous (non-classical) dynamics, and unpredictable properties. It is within this context that this thesis aims to examine the effects of NP geometry and …
Solution And Surface Properties Of Architecturally- And Compositionally-Complex Block Copolymers And Their Binary Mixtures, Jesse Lawrence Davis
Solution And Surface Properties Of Architecturally- And Compositionally-Complex Block Copolymers And Their Binary Mixtures, Jesse Lawrence Davis
Doctoral Dissertations
The spontaneous generation of complex structures from polymeric building blocks provides a simple yet effective route to create useful soft matter structures having potential application in a variety of nanotechnologies. The topology, chemical structure, block composition, and sequence of the constituent building blocks of polymers are tunable through synthetic chemistry. This tunability offers attractive opportunities to generate complex, yet well-defined structures with control over the geometry, packing symmetry, and microdomain structure. This thesis work involves the study of the self-assembly behaviors of architecturally complex amphiphilic block copolymers (ABCs). ABCs are composed of two or more chemically distinct blocks that are …
Novel Thermoplastic Elastomers Based On Benzofulvene: Synthesis And Mechanical Properties, Weiyu Wang
Novel Thermoplastic Elastomers Based On Benzofulvene: Synthesis And Mechanical Properties, Weiyu Wang
Doctoral Dissertations
Thermoplastic elastomers (TPEs) are of great importance both academically and technologically. Currently TPEs are the predominated form of styrene-diene copolymers. However, these styrenic TPEs have serious limitations in applications, especially at higher temperature, because of their low upper service temperature (UST). The work described in this dissertation aimed to developing thermoplastic elastomers with a higher UST and lower cost.
In order to develop TPEs with a higher UST, we employed benzofulvene, an anionically polymerizable monomer in hydrocarbon solvent at room temperature, as the glassy block and copolymerized it with isoprene to prepare polybenzofulvene-polyisoprene-polybenzofulvene (FIF) triblock copolymers. Among all triblock copolymers …
All-Acrylic Multigraft Copolymers: Synthesis And Structure-Property Relationship For Producing Next Generation Thermoplastic Elastomers, Andrew Brown Goodwin
All-Acrylic Multigraft Copolymers: Synthesis And Structure-Property Relationship For Producing Next Generation Thermoplastic Elastomers, Andrew Brown Goodwin
Doctoral Dissertations
Polymer architecture and the advancement of molecular design using anionic and other controlled polymerization methods continues to be of significant research interest because of the tunable approach it provides, which can impact numerous applications ranging from thermoplastics to drug delivery systems. Among the numerous branched structures currently investigated, comb and graft copolymers continue to provide tailored materials which exhibit superior mechanical properties when compared to their di- and triblock linear counterparts. More specifically, the incorporation of two or more monomers into graft and multigraft constructions where the side chains are composed of a plastic (high Tg [glass transition temperature]) …
The Effect Of Composition And Architecture On Polymer Behavior In Homopolymer Blends And Inter-Filament Bonding In 3d Printed Models, Edward Roy Duranty
The Effect Of Composition And Architecture On Polymer Behavior In Homopolymer Blends And Inter-Filament Bonding In 3d Printed Models, Edward Roy Duranty
Doctoral Dissertations
This dissertation presents work that increases our understanding of the effects of composition and architecture on copolymer structure and dynamics and how they affect material diffusion between filaments in a 3D printed model. Copolymers are polymer chains made up of at least two different monomers. The ordering and arrangement of the two monomer species within a copolymer can have drastic effects on the behavior and properties of the copolymer.
The first chapter of this dissertation examines how the copolymer composition affects the structure and dynamics of the chain in a homopolymer blend. This study used a modified Monte Carlo BFM …
Preparation And Characterization Of Thermodynamically Controlled Polymer Nanocomposites, Jiadi Hou
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 …
Siloxane And Silane-Functionalized Polynorbornenes As Membranes For Passive Carbon Dioxide Separation, Eunice Koheun Hong
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 …
Ion Transport In Polymer Electrolytes, Fei Fan
Ion Transport In Polymer Electrolytes, Fei Fan
Doctoral Dissertations
Batteries with superior performance will advance many technologies, such as the field of energy storage and electrochemical devices. Traditional lithium ion batteries based on liquid electrolytes have intrinsic problems such as leaking, dendrite growth, and those problems are associated with fire or even explosion hazard. Extensive efforts have been devoted into the development of solid polymer electrolytes (SPEs), which would not only reduce the size and weight of the batteries, but also solve safety related issues. However, none of current dry SPEs have reached the desired conductivity of 10-3 [0.001] S/cm at ambient temperature. The ion conductivity is controlled …
Biodegradable Nano-Hybrid Polymer Composite Networks For Regulating Cellular Behavior, Charles Henley Sprague
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 …
Polymer Additives Effects On Structure And Dynamics, Adam Eugene Imel
Polymer Additives Effects On Structure And Dynamics, Adam Eugene Imel
Doctoral Dissertations
This dissertation presents work that expands the understanding of the effect additives have on the structure and dynamics of a polymer matrix. Polymer additives are molecules, nanoparticles or fibers that are added to a polymer to modify the properties of the host polymer. Due to the vast amount of additives available, our studies were limited to C60 (C60), soft polystyrene nanoparticles, and poly(ethylene oxide).
The first part of this project examined the influence that C60 nanoparticles have on the assembly of polyacrylonitrile using small angle and wide-angle x-ray scattering techniques and viscometry. The addition of C60 (C60) …
Correlating Morphology To Performance In Conjugated Polymer Nanocomposite Thin Films, Siddharth Pradhan
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 …
Composition Dependence Of The Flory-Huggins Interaction Parameter In Polymer Blends: Structural And Thermodynamic Calculations, Travis H. Russell
Composition Dependence Of The Flory-Huggins Interaction Parameter In Polymer Blends: Structural And Thermodynamic Calculations, Travis H. Russell
Doctoral Dissertations
Flory-Huggins Theory has been the basis for understanding polymer solvent and blended polymer thermodynamics for much of the last 60 years. Within this theory, a parameter (χ) [chi] was included to quantify the enthalpic energy of dispersion between distinct components. Thin film self-assembly of polymer melts and block copolymers depends critically on this parameter, and in application, χ has generally been assumed to be independent of the concentrations of the individual components of the system. However, Small-Angle Neutron Scattering data on isotopic polymer blends, such as polyethylene and deuterated polyethylene, have shown a roughly parabolic concentration dependency for …
Ab Initio Studies Of Proton Transport In Proton Exchange Membranes, Jeffrey Keith Clark
Ab Initio Studies Of Proton Transport In Proton Exchange Membranes, Jeffrey Keith Clark
Doctoral Dissertations
A molecular-level understanding of the factors that contribute to transport properties of proton exchange membranes (PEMs) for fuel cell applications is needed to aid in the development of superior membrane materials. Ab initio electronic structure calculations were undertaken on various PEM ionomer fragments to explore the effects of local hydration, side chain connectivity, protogenic group separation, and specific side chain chemistry on proton dissociation and transfer at low hydration. Cooperative interactions between both intra- and inter-molecular acidic groups and hydrogen bond connectivity were found to enhance proton dissociation at very low degrees of hydration. The energetics associated with proton transfer …
A Study In Conjugated Polymers: From Solution Properties Of P3ht To Synthesis Of Highly Functionalized Conjugated Polymers; Moving Toward Block Copolymers And Beyond, Justin Taylor Roop
A Study In Conjugated Polymers: From Solution Properties Of P3ht To Synthesis Of Highly Functionalized Conjugated Polymers; Moving Toward Block Copolymers And Beyond, Justin Taylor Roop
Doctoral Dissertations
Conjugated polymers have been the focus of intense research for more than a decade now, and advances in this field are beginning to materialize in the production of high-efficiency opto-electronic materials that may led to the generation of energy without the need for fossil fuels. However, these current materials have not been shown to be capable of reaching efficiency levels high enough to be competitive with the siliconbased solar cells that are the standard today. We embarked on a journey in this work to help the next step in conjugated polymer research be attained. We have done just that through …
A Method To Control Morphology Of Bhj Opvs Using End-Functionalized Poly(3-Hexylthiophene)(P3ht) Grafted To Sqds, William Michael Kochemba
A Method To Control Morphology Of Bhj Opvs Using End-Functionalized Poly(3-Hexylthiophene)(P3ht) Grafted To Sqds, William Michael Kochemba
Doctoral Dissertations
Improving the power conversion efficiency of organic photovoltaic devices based on polymer-nanoparticle bulk heterojunctions remains a significant challenge that limits the commercial production of these technologies. There are a number of factors that contribute to the efficiency of photovoltaic devices including absorption, charge generation and charge separation, which ultimately rely on the morphology of the bulk heterojunction active layer. My work aims to improve these processes by developing a method to prepare end-group functionalized π[pi]- conjugated polymers that will be used to decorate the surface of nanoparticles thereby tailoring the interface between the polymer and the nanoparticle. This work involves …
Characterizing The Morphology Of Solvent Annealed Pcbm/P3ht Bilayers Using Gixrd And Raman Spectroscopy, Tyler Evan Mcpherson
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 …