Experimental Evaluation Of Mesh Size In Physically Crosslinked Polymer Gels Using Dynamic Light Scattering, Duncan M. Hill

Honors Theses

Block copolymer gels are under consideration as drug delivery patches. Controlling and modeling the transport inside the gel is an important contribution to the successful delivery of pharmaceuticals. The diffusive transport of a solute – such as a therapeutic compound – within the gel can be described by the mesh size of the gel, which is defined as the distance between polymer chains. Existing experimental evaluations of mesh size do not work for block copolymer gels due to differences in the fundamental gel structure. As such, an experimental method of measuring mesh size of block copolymer gels using dynamic light …

Elucidating The Mechanical And Transport Properties Of Lignin-Based Hydrogel Composites, Nicholas Gregorich

All Dissertations

The use of lignin in the fabrication of soft composites has become an emerging area of research in polymer science and polymer chemistry. These lignin-based materials present numerous benefits, notably, a reduction in the use of petroleum-based precursor, improved structural benefits to otherwise soft host polymers, as well as the inherent antimicrobial and antioxidant properties of lignin, making it suitable for biomaterials. Herein, we present two chemical reaction pathways of incorporating lignin that was fractionated and cleaned using the Aqueous Lignin Purification with Hot Agents (ALPHA) process into poly(vinyl alcohol) (PVA) hydrogel composites for aqueous-based separations. By leveraging the ALPHA …

Poly(Ether Imide)S: Synthesis And Properties, Rachel Price

Honors College Theses

The synthesis of strong polymers is crucial to the creation of heat-resistant, durable, and mechanically useful plastics that we use every day. Poly(ether imide)s are used in applications such as food service, aerospace, automotive, and many more. This thesis will discuss the synthesis and properties of these plastics to help express a larger understanding of these polymers.

Programming The Properties Of Branched Polymers Through Precision Architectures, Michael R. Dearman

LSU Master's Theses

The glass transition of branched polymers is determined by multiple structural parameters that dictate their inter- and intramolecular interactions, and ultimately, their molecular packing in the amorphous phase. Here we examined the impact of side chain length, backbone length, molecular weight composition, and topology on the glass transition behavior of bottlebrush polymers. Through examining precision bottlebrush polymer libraries (PBP, ĐSC = 1.0), we find the infinite molecular weight Tg is reached at a specific brush length after which the effect of the side-chain length dominates. Being a factor more dominant than the backbone, side-chain length affects the Tg of bottlebrush …

Contact Dewatering Of Cellulose Nanofibers For Biopolymer Composite Applications, Alexander Collins

Electronic Theses and Dissertations

Cellulose Nanofibrils (CNFs) are promising materials for reinforcement of polymer matrices attributable to their impressive physical and mechanical properties, as well as their biodegradability. However, the utilization of these materials in composites is made challenging by the water content of CNF slurries, the tendency of CNFs to agglomerate as they dry, and incompatibility between hydrophilic CNFs and hydrophobic polymer matrices. The most commercially viable drying methods to produce small-scale dry CNFs, such as spray drying, are very energy intensive, can only dry the materials down to micron-scale agglomerates, and do not preserve fibrillar aspect ratios. “Contact dewatering,” or the removal …

Therapeutic Injectable Iron-Chelating Hydrogels, Debbie Campbell-Rance

Theses and Dissertations

ABSTRACT

Therapeutic Injectable Iron-Chelating Hydrogels for Improved Central Nervous System Regeneration

By

Debbie S. Campbell-Rance

A dissertation submitted in partial fulfillment of the requirements of the degree of Doctor of Philosophy at Virginia Commonwealth University 2021.

Director: Xuejun Wen, M.D., Ph.D., AIMBE Fellow, Alice T. and William H. Goodwin Jr. Endowed Chair Professor in Regenerative Medicine, Institute for Engineering and Medicine, Department of Chemical and Life Science Engineering

Severe traumatic brain and spinal cord injuries are major global public health and socioeconomic problems in terms of mortality and morbidity. Currently there are two main lines of treatment under development for …

Application Of Sla 3d Printing For Polymers, Taylor Wilson

Williams Honors College, Honors Research Projects

Stereolithography is a type of 3D printing that allows liquid photopolymer resin to be cured into layers that make up a 3D object. Creation of such resins for these purposes can require a significant amount of time to test and develop, and commercial resins also require some amount of testing for printer settings before use. This paper reviews how stereolithography works, the materials used, and experimentation done to compare the resin properties to the determined curing times. Using several commercially available resins, varying base exposure and layer exposure times were used to determine the lowest possible curing time that gave …

Approaching Disorder-Tolerant Semiconducting Polymers, Xinwen Yan, Miao Xiong, Xin Yu Deng, Kai Kai Liu, Jia Tong Li, Xue Qing Wang, Song Zhang, Nathaniel Prine, Zhuoqiong Zhang, Wanying Huang, Yishan Wang, Jie Yu Wang, Xiaodan Gu, Shu Kong So, Jia Zhu, Ting Lei

Faculty Publications

Doping has been widely used to control the charge carrier concentration in organic semiconductors. However, in conjugated polymers, n-doping is often limited by the tradeoff between doping efficiency and charge carrier mobilities, since dopants often randomly distribute within polymers, leading to significant structural and energetic disorder. Here, we screen a large number of polymer building block combinations and explore the possibility of designing n-type conjugated polymers with good tolerance to dopant-induced disorder. We show that a carefully designed conjugated polymer with a single dominant planar backbone conformation, high torsional barrier at each dihedral angle, and zigzag backbone curvature is highly …

Electrospinning Fibers Via Complex Coacervation, Xiangxi Meng

Doctoral Dissertations

Electrospun fibers are high-surface-area materials widely used in applications ranging from batteries to wound dressings. Typically, an electrospinning precursor solution is prepared by dissolving a high-molecular-weight polymer in an organic solvent to form a sufficiently entangled solution. Our approach bypasses the requirement for entanglements and completely avoids toxic chemicals by focusing on using an aqueous complex coacervates solution. Coacervates are a dense, polymer-rich liquid phase resulting from the associative electrostatic complexation of oppositely charged macroions. We were the first to demonstrate that liquid complex coacervates could be successfully electrospun into polyelectrolyte complex (PEC) fibers. A canonical coacervate system was formed …

Establishing Independent Tunability Of The Mechanical And Transport Properties Of Polymer Gels, Lucas Rankin

Master’s Theses

Polymer gels can be used in the fabrication of materials for filtering liquid and gaseous media, solid-state electrolytes, and transdermal medical patches. This diverse range of applications primarily relies on the transport and mechanical properties of polymer gels. Both sets of properties have shown excellent tunability, but typically in a coupled fashion. Establishing the independent tunability of the transport and mechanical properties of polymer gels (using simple, cost-effective methods) is paramount if polymer gels are to be used to their full potential. Specifically, block copolymer gels self-assemble into organized nanoscale networks within the gel solvent, which allows for facile control …

Methods For Film Coating Electrospun Fibers, Kristopher Dejean

Williams Honors College, Honors Research Projects

Electrospinning uses high voltages to form polymer nanofiber membranes. These membranes have potential for use in filtration, tissue engineering, drug delivery, and catalysis. The nonwoven fiber mat is malleable but has a low tensile strength compared to a solid film of the same polymer. Joining the fibers with a thin film is desired to balance the strength and flexibility. Three methods of producing a film on fiber membrane were tested. The techniques are spraying then melting, spin coating, and dip coating. Electrospinning setup conditions, solvent ratios, damage to fibers, and spin coating speeds were determined. Research was abruptly stopped and …

Kinetics And Dynamics Of Electrophoretic Translocation Of Polyelectrolytes Through Nanopores, Harshwardhan Katkar

Doctoral Dissertations

The idea of sequencing a DNA based on single-file translocation of the DNA through nanopores under the action of an electric field has received much attention over the past two decades due to the societal need for low cost and high-throughput sequencing. However, due to the high speed of translocation, interrogating individual bases with an acceptable signal to noise ratio as they traverse the pore has been a major problem. Experimental facts on this phenomenon are rich and the associated phenomenology is yet to be fully understood. This thesis focuses on understanding the underlying principles of polymer translocation, with an …

A Label-Free High Throughput Resistive-Pulse Sensor For Simultaneous Differentiation And Measurement Of Multiple Particle-Laden Analytes, Ashish Jagtiani, Rupesh Sawant, Jiang Zhe

Dr. Jiang Zhe

We describe an all-electronic, label-free, resistive-pulse sensor that utilizes multiple microchannels for parallel detection, counting and differentiation of multiple biological particles simultaneously. Four particle solutions, including 20 µm and 40 µm polymethacrylate particles, Juniper Scopulorum (Rocky Mountain Juniper) pollen and Populus deltidoes (Eastern Cottonwood) pollen, were loaded to the four peripheral reservoirs, respectively, and were driven to the central reservoir through four microchannels, all operating simultaneously for particle detection and counting. Experiments demonstrated that this sensor was able to differentiate and count multiple particle solutions simultaneously through its four microchannels fabricated on polymer membranes. Thus the sensing throughput has been …

Polymer Based Nanocomposites With Nanofibers And Exfoliated Clay, Michael Meador, Darrell Reneker

Darrell Hyson Reneker

Polymer solutions, containing clay sheets, were electrospun into nanofibers and microfibers that contained clay sheets inside. Controllable removal of polymer by plasma etching from the surface of fibers revealed the arrangement of clay. The shape, flexibility, size distribution and arrangement of clay sheets were observed by transmission and scanning electron microscopy. The clay sheets were partially aligned in big fibers with normal direction of clay sheets perpendicular to fiber axis. Crumpling of clay sheets inside fibers was observed when the fiber diameter was comparable to the lateral size of clay sheets. Single sheets of clay were observed both by catching …

Spectroscopic Investigation Into Oxidative Degradation Of Silica-Supported Amine Sorbents For Co2 Capture, Chakravartula Srikanth, Steven Chuang

Steven S.C. Chuang

Oxidative degradation characteristics of silica-supported amine sorbents with varying amounts of tetraethylenepentamine (TEPA) and polyethylene glycol (PEG; P200 or P600 represents PEG with molecular weights of 200 or 600) have been studied by IR and NMR spectroscopy. Thermal treatment of the sorbents and liquid TEPA at 100 °C for 12 h changed their color from white to yellow. The CO2 capture capacity of the TEPA/SiO2 sorbents (i.e., SiO2-supported TEPA with a TEPA/SiO2 ratio of 25:75) decreased by more than 60 %. IR and NMR spectroscopy studies showed that the yellow color of the degraded sorbents resulted from the formation of …

Application Of The Thermal Flash Technique For Low Thermal Diffusivity Micro/Nanofibers, Michael T. Demko, Zhenting Dai, Han Yan, William P. King, Miko Cakmak, Alexis R. Abramson

Mukerrem Cakmak

The thermal flash method was developed to characterize the thermal diffusivity of micro/nanofibers without concern for thermal contact resistance, which is commonly a barrier to accurate thermal measurement of these materials. Within a scanning electron microscope, a micromanipulator supplies instantaneous heating to the micro/nanofiber, and the resulting transient thermal response is detected at a microfabricated silicon sensor. These data are used to determine thermal diffusivity. Glass fibers of diameter 15 mu m had a measured diffusivity of 1.21x10(-7) m(2)/s; polyimide fibers of diameters 570 and 271 nm exhibited diffusivities of 5.97x10(-8) and 6.28x10(-8) m(2)/s, respectively, which compare favorably with bulk …

Aging Of A Polymer Core Composite Conductor Under Combined Ozone And Temperature Conditions, James M. Middleton

Electronic Theses and Dissertations

The next generation High Temperature Low Sag Polymer Core Composite Conductors (HTLS PCCC) can experience harsh in-service environments including high temperature and highly concentrated ozone. In some extreme cases, it is possible that the conductors will experience temperatures of up to 180°C and ozone concentrations as high as 1% (10,000 ppm). Therefore, the primary goal of this research was to determine the most damaging aging conditions which could negatively affect the in-service life of the conductors. This included characterizing the aging in ozone and at high temperature of the HTLS PCCC hybrid composite rods and neat resin. It was found …

Plasma Processes And Polymers Special Issue On: Plasma And Cancer, Mounir Laroussi, Michael Keidar

Electrical & Computer Engineering Faculty Publications

During the last two decades, research efforts on the application of low temperature plasmas in biology and medicine have positioned nonequilibrium lowtemperature plasmas as a technology that has the potential of revolutionizing healthcare.[1,2] Low temperature plasmas can be applied in direct contact with living tissues to inactivate bacteria,[3] to disinfect wounds and accelerate wound healing,[4] and to induce damage in some cancer cells.[5–11]

Production Of Lignin-Based Phenolic Resins Using De-Polymerized Kraft Lignin And Process Optimization, Homaira Siddiqui

Electronic Thesis and Dissertation Repository

Commercialization of Lignin-based phenol formaldehyde resins (LPF) has been limited due to the increase in curing temperatures and decrease in adhesive strength of LPF compared to conventional phenolic resins. Lignin depolymerization can increase the reactivity of lignin; however, the effect of lignin molecular weight on curing performance of LPF resins has yet to be investigated. This research work examined the optimization of synthesis parameters including percent substitution of phenol with lignin, formaldehyde- to-phenol ratio (F/P), and Mw of lignin to reduce the curing temperature and increase the adhesive strength of LPF. DSC analysis indicated that lignin with Mw ~1200g/mol resulted …

Developing Reactive Molecular Dynamics For Understanding Polymer Chemical Kinetics, Kenneth D. Smith

Open Access Dissertations

One of the challenges in understanding polymer flammability is the lack of information about microscopic events that lead to macroscopically observed species, and Reactive Molecular Dynamics is a promising approach to obtain this crucially needed information. The development of a predictive method for condensed-phase reaction kinetics can provide significant insight into polymer ammability, thus helping guide future synthesis of fire-resistant polymers. Through this dissertation, a new reactive forcefield, RMDff, and Reactive Molecular Dynamics program, RxnMD, have been developed and used to simulate such material chemistry. It is necessary to have accurate description of chemical kinetics to describe quantitative chemical kinetics. …

Application Of The Thermal Flash Technique For Low Thermal Diffusivity Micro/Nanofibers, Michael T. Demko, Zhenting Dai, Han Yan, William P. King, Miko Cakmak, Alexis R. Abramson

College of Polymer Science and Polymer Engineering

The thermal flash method was developed to characterize the thermal diffusivity of micro/nanofibers without concern for thermal contact resistance, which is commonly a barrier to accurate thermal measurement of these materials. Within a scanning electron microscope, a micromanipulator supplies instantaneous heating to the micro/nanofiber, and the resulting transient thermal response is detected at a microfabricated silicon sensor. These data are used to determine thermal diffusivity. Glass fibers of diameter 15 mu m had a measured diffusivity of 1.21x10(-7) m(2)/s; polyimide fibers of diameters 570 and 271 nm exhibited diffusivities of 5.97x10(-8) and 6.28x10(-8) m(2)/s, respectively, which compare favorably with bulk …

Structure Property Relationships In Electron Donating Systems For Potential Photovoltaic Applications., Jonathan Moghal

Doctoral

Conjugated polymers are considered to be one-dimensional semiconductors. In conjugated polymers single and double bonds alternatively bond the carbon atoms along the polymer chain. The loosely bound electrons determine the electronic properties of conjugated polymers. In order to utilise the properties of conjugated polymers in terms of a photovoltaic (PV) device application an acceptor material must be added. The acceptor material used in this study is used in buckminsterfullerence (C60). C60 was selected for this purpose due to its size and the fact that it can accept up to six additional electrons. Ultrafast charge transfers from a conducting polymer onto …

Energetic And Entropic Elasticity Of Nonisothermal Flowing Polymers: Experiment, Theory, And Simulation, T. C. Ionescu, B. J. Edwards, David Keffer, V. G. Mavrantzas

Faculty Publications and Other Works -- Chemical and Biomolecular Engineering

The thermodynamical aspects of polymeric liquids subjected to nonisothermal flow are examined from the complementary perspectives of theory, experiment, and simulation. In particular, attention is paid to the energetic effects, in addition to the entropic ones, that occur under conditions of extreme deformation. Comparisons of experimental measurements of the temperature rise generated under elongational flow at high strain rates with macroscopic finite element simulations offer clear evidence of the persistence and importance of energetic effects under severe deformation. The performance of various forms of the temperature equation are evaluated with regard to experiment, and it is concluded that the standard …

Energetic And Entropic Elasticity Of Nonisothermal Flowing Polymers: Experiment, Theory, And Simulation, David Keffer, T. C. Ionescu, B. J. Edwards, V. G. Mavrantzas

David Keffer

The thermodynamical aspects of polymeric liquids subjected to nonisothermal flow are examined from the complementary perspectives of theory, experiment, and simulation. In particular, attention is paid to the energetic effects, in addition to the entropic ones, that occur under conditions of extreme deformation. Comparisons of experimental measurements of the temperature rise generated under elongational flow at high strain rates with macroscopic finite element simulations offer clear evidence of the persistence and importance of energetic effects under severe deformation. The performance of various forms of the temperature equation are evaluated with regard to experiment, and it is concluded that the standard …

Phase Behavior In Copolymer Blends Of Poly(P-Chlorostyrene-Co-O-Chlorostyrene) And Phenylsulfonylated Poly(2,6-Dimethyl-1,4-Phenylene Oxide), William Macknight, R. Vukovic, G. Bogdanic, Vjera Kuresevic, M. Tomaskovic, F. E. Karasz

William MacKnight

Thermodynamic Aging Of Immiscible Polymer Blends, William Macknight, Ronald Koningsveld, Karel Sole

William MacKnight

No abstract provided.

The Effects Of Low Doses (1 To 500 Kilograys) Of 100-Kev Electrons On Four Polymers, Cynthia Anne Bradbury

Physics Theses & Dissertations

Commercial films of polyetherimide (PEI), polyetheretherimide (PEEI), polyethylene terephthalate (PET), and polycarbonate (PC) were exposed in vacuum to l 00-keV electron radiation to total absorbed doses of l, l 0, l 00, 300, and 500 kilograys. The concentration of radiation-generated radicals, as measured by electron paramagnetic resonance (EPR), increased by over an order of magnitude in all four polymers. Correspondingly, the intensity of the infrared absorption peaks increased uniformly for all doses. Solubility tests resulted in decreased solubility in all polymers. IR, EPR, and solubility suggest dehydrogenation of the aliphatic C-H and phenyl C-H sites. The data indicated that cross …

Molecular Motions In Model Network Polymers, William Macknight, L. Charles Dickinson, P. Morganelli, C. W. Chu, Z. Petrovic, James C. W. Chien

William MacKnight

No abstract provided.

Structure And Applications Of Ion-Containing Polymers, William Macknight

William MacKnight

No abstract provided.

Deformation Studies Of Polymers By Time-Resolved Infrared Spectroscopy Iv: A Modified Approach, William Macknight, S. E. Moles, S. L. Hsu

William MacKnight

No abstract provided.