Polymer Science Commons^™

Role Of Nitrogenous Functional Group Identity In Accelerating 1,2,3- Trichloropropane Degradation By Pyrogenic Carbonaceous Matter (Pcm) And Sulfide Using Pcm-Like Polymers, Han Cao, Jingdong Mao, Paul G. Tratnyek, Wenqing Xu

Chemistry & Biochemistry Faculty Publications

Groundwater contamination by 1,2,3-trichloropropane (TCP) poses a unique challenge due to its human toxicity and recalcitrance to degradation. Previous work suggests that nitrogenous functional groups of pyrogenic carbonaceous matter (PCM), such as biochar, are important in accelerating contaminant dechlorination by sulfide. However, the reaction mechanism is unclear due, in part, to PCM's structural complexity. Herein, PCM-like polymers (PLPs) with controlled placement of nitrogenous functional groups [i.e., quaternary ammonium (QA), pyridine, and pyridinium cations (py⁺)] were employed as model systems to investigate PCM-enhanced TCP degradation by sulfide. Our results suggest that both PLP-QA and PLP-py⁺ were highly effective …

Robust Gasification Trial Results For A Variety Of Difficult-To-Recycle Packaging-Related Materials, Bruce A. Welt

Journal of Applied Packaging Research

Currently, recycling requires nearly absolute sorting of materials to accommodate the limited capabilities of existing recycling infrastructure. Whether a material is “recyclable” depends more on the method of recycling than the material itself. Our dependence upon sorting has limited success of recycling and has stifled our ability to achieve circular economy sustainability with plastic packaging materials. Our dependence upon sorting is rooted in our material-specific recycling processes. However, newer robust recycling processes are commercially available that reduce or eliminate the need to sort waste, and can convert mixed waste into primary feedstock chemicals, such as methanol for subsequent manufacture of …

Using Afm-Ir To Study Nanoscopic Phase Behavior Of Polymer Blends And Photovoltaic Bulk Heterojunctions, Nathaniel L. Prine

Dissertations

Conjugated polymers (CPs) and polymer blends harbor the potential for high-performance organic solar cells (OSCs) due to their short energy payback time, low cost, solution processability, lightweight attributes, and flexibility. However, OSCs suffer from poor thermal stability compared to their inorganic equivalents. This study explores the thermal instability of OSCs, focusing on phase separation of the photoactive layer under heat, resulting in morphology changes and degradation of power conversion efficiency (PCE). Utilizing atomic-force microscopy coupled with infrared spectroscopy (AFM-IR) and differential scanning calorimetry (DSC), we delve into thermal stability-morphology relationships to devise strategies to improve OSC blend durability under thermal …

Amine-Functionalized Lignin-Based Ionomer Nanocomposites For Redox Flow Batteries, Joshua Wilder

All Theses

As the development of energy storage technologies for renewable energy sources continues to garner attention, vanadium redox flow batteries (VRFBs) have emerged as promising source for grid-scale energy storage. A major component of the VRFB is the ion exchange membrane (IEM), as it serves to physically separate the two liquid electrolytes and also directly impacts the battery’s capacity, efficiency, and cost. The current industry standard IEM, Nafion™, not only accounts for a large portion of the cost of the VRFB but also suffers from poor proton selectivity. Herein, we have synthesized sulfonated poly(ether ether ketone) (SPEEK) composite membranes containing amine …

Characterization Of Interlayer Laser Shock Peening During Fused Filament Fabrication Of Polylactic Acid (Pla), Fabien Denise

Department of Mechanical and Materials Engineering: Dissertations, Theses, and Student Research

The field of additive manufacturing (AM) has gained a significant amount of popularity due to the increasing need for more sustainable manufacturing techniques and the adaptive development of complex product geometries. The problem is that AM parts routinely exhibit flaws or weaknesses that affect functionality or performance. Over the years, surface treatments have been developed to compensate certain flaws or weaknesses in manufactured products. Combining surface treatments with the modularity of additive manufacturing could lead to more adaptable and creative improvements of product functions in the future. The current work evaluates the feasibility of pursuing a new research axis in …

Development Of Lignin-Based Copolymers And Polymer Blends, David Chem

Graduate Theses and Dissertations

Increasing industrial interest in reducing fossil fuels in virgin polymer production and incorporating bio-based polymeric materials has led researchers to explore the potential of utilizing plant-based polymers such as lignin. Chapter 1 of this thesis presents a comprehensive overview of copolymerization and blending techniques for lignin and synthetic polymers, emphasizing different types of modifications and copolymerization techniques as well as key parameters such as temperature, reaction time, pH level, and solution compositions. These valorization methods are directed towards the development of high-value lignin-based materials with properties well-suited for various commercial applications. Chapter 2 offers a fundamental exploration into the amination …

Influence Of Metal-Coordinating Comonomers On The Coordination Structure And Binding In Magnetic Poly(Ionic Liquid)S, Kayla Foley, Lucas Condes, Keisha B. Walters

Chemical Engineering Faculty Publications and Presentations

A poly(ionic liquid) (PIL), poly(acrylamide-co-diallyl dimethylammonium chloride), was systematically complexed with Co²⁺, Fe³⁺, and Co²⁺/Fe³⁺ (mixed) at different molar equivalencies to form a series of magnetic PILs (MPILs). These novel MPILs were utilized to examine molecular structure and binding between the polymer and metal species using comprehensive spectroscopic studies in both dry and liquid states. FTIR, X-ray photoelectron, UV-vis, and Raman spectroscopies showed evidence of metal coordination of both the iron and cobalt chloride species with the acrylamide comonomer. Using AC susceptibility measurements, the MPILs were found to have magnetic properties …

Cellulose Materials For Drug Delivery Applications, Reham Mohamed

Mechanical Engineering Theses

Non-healing wounds are a growing global public health concern due to inadequate or ineffective therapeutic products available. Cellulose-based biopolymers are attractive wound dressing materials due to their biocompatibility, biodegradability, non-toxicity, and cost-effectiveness. This study aims to design and fabricate solid dosage formulations using carboxymethyl cellulose (CMC) and ethyl cellulose (EC) to facilitate multi-stage releases of phenytoin (PHT) and tetracycline hydrochloride (TCH) from plain carriers, fibers/films composites, and layer-by-layer fiber composites. Results from in vitro drug release assays demonstrated a time-dependent release up to 8 hours from PHT-loaded EC fibers, while TCH-loaded CMC films exhibited a rapid release within 5 minutes. …

Engineering Of Functionalized Carbon Nano-Onions Embedded Bsa Nanocomposite Fibers For Stimuli-Responsive Drug Release, Ramiro Manuel Velasco Delgadillo, Narsimha Mamidi

Research Symposium

Background: Advanced drug delivery systems (DDSs) have received enormous attention in biomedical applications due to their pharmacodynamic and pharmacokinetic drug properties. For the present study, poly 4-hydroxyphenyl methacrylate (PHPMA)/CNOs (f-CNOs) inserted bovine serum albumin (BSA) nanofibers were prepared for stimuli-responsive release of Doxorubicin (DOX). Temperature and pH would be altered to study the release of DOX in acidic microenvironments.

Methods: PHPMA were coupled with COOH-CNOs via ester coupling via the sonochemical method to produce PHPMA-CNOs (f-CNOs). Then, f-CNOs/DOX embedded BSA nanofibers were prepared at room temperature using Forcespinning. UV spectra of DOX-loaded nanofibers were studied to investigate the …

Solution And Film Self-Assembly Behavior Of A Block Copolymer Composed Of A Poly(Ionic Liquid) And A Stimuli-Responsive Weak Polyelectrolyte, Kayla Foley, Keisha B. Walters

Chemical Engineering Faculty Publications and Presentations

Cu(0)-mediated atom transfer radical polymerization was used to synthesize a poly(ionic liquid), poly[4-vinylbenzyl-3-butylimidazolium bis(trifluoromethylsulfonyl)imide] (PVBBImTf₂N), a stimuli-responsive polyelectrolyte, poly[2-(dimethylamino)ethyl methacrylate] (PDMAEMA), and a novel block copolymer formed from these two polymers. The synthesis of the block copolymer, poly[2-(dimethylamino) ethyl methacrylate]-block-[poly(4-vinylbenzyl-3-butylimidazolium bis(trifluoromethylsulfonyl)imide] (PDMAEMA-b-PVBBImTf₂N), was examined to evaluate the control of “livingness” polymerization, as indicated by molecular weight, characterizations of degree of polymerization, and ¹HNMR spectroscopy. 2D DOSY NMR measurements revealed the successful formation of block copolymer and the connection between the two polymer blocks. PDMAEMA-b-PVBBImTf₂N was further characterized …

Investigating The Rheological Behavior Of A Simple Yield Stress Fluid Under Shear Flows, Francesco Accetta

Theses

Many soft materials display unique and complex rheological behavior characterized by a transition from a solid-like to a fluid-like state upon the application of a force that exceeds the threshold to flow, known as the yield stress. Yield stress fluids are found in a wide range of commonly encountered materials including microgels, emulsions, and foams, and have been widely studied by rheologists over the last several decades. Carbopol is a popular polymeric microgel system as it displays simple, non-thixotropic rheological behavior and is typically seen as an ideal yield stress fluid. Previous research has demonstrated the reproducible behavior of shear …

Retracted: Fabrication And Characterization Of Wood Fiber Reinforced Polymer Composites, Firoz Ahmed, Omar Faroque, Saif Hasan, Khan Rajib Hossain, Rezaul Karim Sheikh

Al-Bahir

Wood-polymer composites (WPCs) combine the properties of wood and polymers. Creating composites involves adding plant or wood fibers as fillers to a polymer matrix. This study used mahogany and mango wood sawdust as reinforcement materials, while high-density polyethylene (HDPE) and polyvinyl chloride (PVC) were used as matrices. The investigated data in this study comprises four different (10, 20, 30, and 40) weight percentages (wt%) of mahogany and mango sawdust paired with corresponding wt% (90, 80, 70, and60) of HDPE and PVC matrices. The extrusion method produced composites with different amounts of sawdust and polymer matrices. Wood polymer composites were characterized …

The Cosolvent And Association Effect On Polymer Behaviors, Xiangyu Zhang

Theses and Dissertations

The blending or mixing is extensively utilized in diverse processes of polymers to bring about advantageous properties, but the behavior becomes intriguing when associations are involved and multi-solvents are used. Explanations based on chemistry-specific arguments are less than satisfactory in abstracting essential features, and lack the general applicability across various systems. So, this work focuses on capturing the physical force governing the phenomenon of interest by using a generic model. Highly non-trivial behaviors of polymers are often observed in multi-solvent solutions. It is known that polymers swell and dissolve in good solvents, while they tend to collapse and aggregate in …

Designing Bioinspired Materials With Tunable Structures And Properties From Natural And Synthetic Polymers, Anandavalli Varadarajan

Theses and Dissertations

Biological systems are composed of complex materials which are responsible for performing various functions, such as providing structural support, mobility, functional adaptation to the environment, damage repair, and self-healing. These complex materials display excellent mechanical properties and can rapidly adapt to external stimuli. Thus, nature inspires in terms of source materials, functions, and designs to develop new-generation structural and functional materials. Polymers (natural or synthetic) are excellent sources of developing materials to mimic the functions of soft segments in biological systems. This dissertation focuses on synthesizing and characterizing two different materials with tunable structures and properties: complexes from natural polysaccharides …

Elucidating Self-Assembly Of Semiconducting Polymers In The Presence Of A Low Molecular Weight Gelator, Madhubhashini Lakdusinghe

Theses and Dissertations

Semiconducting polymers with a conjugated backbone are important for energy storage, conversion, and biomedical field applications. The self-assembly process of these polymers in solutions depends on the polymer concentration and quality of the solvent. The electrical properties of thin films obtained from the solution phase depend on the self-assembled process. Thin films of conjugated polymer gels with percolating networks of self-assembled structures display improved electrical conductivities. In this dissertation, we studied the impact of the secondary gel matrix formed by a low molecular weight gelator, on the self-assembly of conjugated polymers, the preservation of assembled structures in dried gel films …

Activated Carbon Synthesis From Lignin-Rich Byproduct Streams Of Biorefineries, Chengjun Wu

All Dissertations

Over the past decade, the production of biofuels from lignocellulosic biomass has steadily increased to offset the use of fuels from petroleum. To make biofuels cost-competitive, it is necessary to add value to the “ligno-” components (up to 30% by mass) of the biomass. Instead of just burning it for heat and electricity generation, direct conversion of lignin carbon into a product provides a complementary path to carbon capture, promoting a more environmentally conscious approach. However, the utilization of these lignin-rich byproduct streams, which are separated from the biofuels production, for industrial products can be challenging. The use of specific …

Improving Lignin Recovery From Paper Mill And Biorefinery Waste Streams Via Liquid-Phase Splitting, Carter Fitzgerald

All Dissertations

Lignin is an abundant biopolymer with significant promise due to its aromaticity. It has been targeted as a replacement for a number of petroleum-based products including adhesives, coatings, polyurethane foams, activated carbon, and carbon fibers. However, commercially available bulk lignins are too polydisperse, and contain too many residual metals from the pulping process that are detrimental to the properties of the final product.

The Sequential Liquid-lignin Recovery and Purification (SLRP) process was developed by Michael Lake and John Blackburn, in collaboration with Clemson, with the intention of creating a continuous method for recovering lignin from paper-mill black liquors. Thies and …

Characterization Of Mechanically Recycled Polylactic Acid (Pla) Filament For 3d-Printing By Evaluating Mechanical, Thermal, And Chemical Properties And Process Performance, Mahsa Shabani Samghabady

All Theses

Polylactic acid (PLA) is a biopolymer made from renewable resources such as sugar and corn. PLA filament is a popular material used in Fused Deposition Modeling (FDM) 3D-printing. While this material has many advantages, all the failed parts, support structures, rafts, nozzle tests, and the many prototype iterations during the 3D-printing process contribute to the plastic pollution and release of greenhouse gases. Although PLA is biodegradable, it can take years to degrade in landfills. Instead of throwing away PLA waste and buying new filaments, PLA can be recycled. Amongst the different recycling technologies, mechanical recycling is the most environmentally friendly. …

Carbon Fibers From Athabasca Oil-Sand Asphaltenes, Blake Reardon

All Theses

Carbon fibers possess ultra-high specific strength and modulus. Therefore, the material is popular in aerospace, automotive, and sports industries. Approximately 95% of all carbon fibers are spun from a high-cost precursor, polyacrylonitrile (PAN). There is a need for a cheaper grade of carbon fiber for low-cost applications because about half of carbon fiber cost is associated with precursor cost. A promising alternative to the high-cost PAN precursor is petroleum-based asphaltene. Asphaltenes are highly aromatic and have a high carbon content but lack the purity of the PAN precursor. Processes like the molten- sodium desulfurization upgrading have been used to harvest …

Development Of Non-Viral Nano-Carriers For Gene Delivery And Covid-19 Vaccines, Zhongyu Li

Dissertations

Gene therapy is one of the most promising medical fields with the potential to effectively advance the treatment of difficult diseases by producing therapeutic proteins or repairing defective gene sequences. However, gene therapy presents severe challenges in delivery including renal clearance, phagocytosis, enzymatic degradation, protein absorption, and cellular internalization barriers, which have been barriers for translation into the clinic. Naked nucleic acids, with their intrinsic negative charge, electrostatically repulse the anionic cell membrane, preventing cellular uptake. Also, they are considered foreign genetic material when introduced into the body and are rapidly cleared by the reticuloendothelial system or degraded by nucleases, …