Polymer and Organic Materials Commons^™

Tailoring Thermoresponsive Poly(N-Isopropylacrylamide) Toward Sensing Perfluoroalkyl Acids, Dustin Thomas Savage

Theses and Dissertations--Chemical and Materials Engineering

Widespread distribution of poly- and perfluoroalkyl substances (PFAS) in the environment combined with concerns for their potentially negative health effects has motivated regulators to establish strict standards for their surveillance. The United States Environmental Protection Agency issued a cumulative domestic threshold of 70 ppt for water supplies, and this bar is even lower in some local districts and other countries. Monitoring PFAS consequently requires sensitive analytical equipment to meet regulatory specifications, and liquid chromatography with tandem mass spectroscopy (LC/MS/MS) is the most common technique used to satisfy these requirements. Though extremely sensitive, the instrument is often burdened by pretreatment regimens, …

Fabrication, Characterization And Applications Of Highly Conductive Wet-Spun Pedot:Pss Fibers, Ruben Sarabia Riquelme

Theses and Dissertations--Chemical and Materials Engineering

Smart electronic textiles cross conventional uses to include functionalities such as light emission, health monitoring, climate control, sensing, storage and conversion of energy, etc. New fibers and yarns that are electrically conductive and mechanically robust are needed as fundamental building blocks for these next generation textiles.

Conjugated polymers are promising candidates in the field of electronic textiles because they are made of earth-abundant, inexpensive elements, have good mechanical properties and flexibility, and can be processed using low-cost large-scale solution processing methods. Currently, the main method to fabricate electrically conductive fibers or yarns from conjugated polymers is the deposition of the …

Nanostructured Metal Thin Films As Components Of Composite Membranes For Separations And Catalysis, Michael J. Detisch

Theses and Dissertations--Chemical and Materials Engineering

Novel metallic thin film composite membranes are synthesized and evaluated in this work for improved separations and catalysis capabilities. Advances in technology that allow for improved membrane performance in solvent separations are desirable for low molecular weight organic separation applications such as those in pharmaceutical industries. Additionally, the introduction of catalytic materials into membrane systems allow for optimization of complex processes in a single step. By adding a nanostructured metallic thin film to its surface, a polymer membrane may be modified to exhibit these improved properties. Using magnetron sputtering, thin metal films may be deposited on commercially available membranes to …

The Fabrication And Characterization Of Metal Oxide Nanoparticles Employed In Environmental Toxicity And Polymeric Nanocomposite Applications, Matthew Logan Hancock

Theses and Dissertations--Chemical and Materials Engineering

Ceria (cerium oxide) nanomaterials, or nanoceria, have commercial catalysis and energy storage applications. The cerium atoms on the surface of nanoceria can store or release oxygen, cycling between Ce³⁺ and Ce⁴⁺, and can therefore act as a therapeutic to relieve oxidative stress within living systems. Nanoceria dissolution is present in acidic environments in vivo. In order to accurately define the fate of nanoceria in vivo, nanoceria dissolution or stabilization is observed in vitro using acidic aqueous environments.

Nanoceria stabilization is a known problem even during its synthesis; in fact, a carboxylic acid, citric acid, is …

Application Of Cross-Linked Polyborosiloxanes And Organically Modified Boron Silicate Binders In Silicon-Containing Anodes For Lithium-Ion Batteries, Darius A. Shariaty, Dali Qian, Yang-Tse Cheng, Susan A. Odom

Chemistry Faculty Publications

To determine the effect of cross-linking in polymer binders on gravimetric capacity and retention in charge/discharge cycling of lithium-ion batteries containing silicon anodes, polymers with a varied chemiophysical characters have been studied as electrode binders. Here we report the utilization of cross-linked polyborosiloxanes and a boron-modified organosilicate as binders for nanoparticulate silicon-containing anodes for lithium-ion batteries. We show that highly cross-linked binders enable a large degree of capacity to be accessed and that capacity retention is greater when the electrodes are cycled in half cells. More extensive analysis of the boron-modified organosilicate is further explored.

Surface Engineering And Monomer Design For Light-Mediated Ring Opening Metathesis Polymerization, Ishan A. Fursule

Theses and Dissertations--Chemical and Materials Engineering

Stimuli-responsive materials are changing the landscape of actuated materials, optoelectronics, molecular machines, solar cells, temporary memory storage, and biomedical materials. Specifically, photo-responsive polymers have gained acceleration in research and application since the last two decades in the form of a surface coating and micro-patterns. Light as a stimulus can be coherent, mono or polychromatic, tunable for power (intensity) and energy (wavelength), and has precise spatiotemporal control. Conventional surface coating techniques such as spin coating are unable to impart properties to the coatings in terms of sturdiness, homogeneity, uniformity over the complex surface, post deposition modification, and process efficiency. Also, in …

Mixed Matrix Flat Sheet And Hollow Fiber Membranes For Gas Separation Applications, Nicholas W. Linck

Theses and Dissertations--Chemical and Materials Engineering

Mixed matrix membranes (MMM) offer one potential path toward exceeding the Robeson upper bound of selectivity versus permeability for gas separation performance while maintaining the benefits of solution processing. Many inorganic materials, such as zeolites, metal-organic frameworks, or carbon nanotubes, can function as molecular sieves, but as stand-alone membranes are brittle and difficult to manufacture. Incorporating them into a more robust polymeric membrane matrix has the potential to mitigate this issue.

In this work, phase inversion polymer solution processing for the fabrication and testing of asymmetric flat sheet mixed matrix membranes was employed with CVD-derived multiwall carbon nanotubes (MWCNTs) dispersed …

Synthesis And Characterization Of Poly(Simvastatin) - Incorporated Copolymers And Blends For Bone Regeneration, Theodora Asafo-Adjei

Theses and Dissertations--Biomedical Engineering

Common biodegradable polyesters such as poly(lactic acid) (PLA), poly(lactic-co-glycolic acid) (PLGA) and poly(ε-caprolactone) (PCL) are used as drug delivery vehicles for tissue regenerative applications. However, they are typically bioinert, with drug loading limitations. Polymerizing the active agent or precursor into its respective biodegradable polymer would control drug loading via molar ratios of drug to initiator used for synthesis. Simvastatin was chosen due to its favorable anti-inflammatory, angiogenic, and osteogenic properties. In addition, its lactone ring lends itself to ring-opening polymerization and, consequently, the synthesis of poly(simvastatin) with controlled simvastatin release.

Simvastatin was first polymerized with a 5kDa methyl-terminated poly(ethylene glycol) …

Functionalization Of Silver Nanoparticles On Membranes And Its Influence On Biofouling, Conor G. Sprick

Theses and Dissertations--Chemical and Materials Engineering

Ultrafiltration (UF) processes are often used as pretreatment before more retentive/costly processes, such as nanofiltration and reverse osmosis. This study shows the results of low-biofouling nanocomposite membranes, loaded with casein-coated silver nanoparticles (casein-Ag-NPs). Membranes were cast and imbedded with Ag-NPs using two approaches, physical blending of Ag-NPs in the dope solution (^PAg-NP/CA membranes) and chemical attachment of Ag-NPs to cast membranes (^CAg-NP/CA membranes), to determine their biofouling control properties. The functionalization of Ag-NPs onto the CA membranes was achieved via attachment with functionalized thiol groups with the use of glycidyl methacrylate (GMA) and cysteamine chemistries. The …

Tunable Nanocomposite Membranes For Water Remediation And Separations, Sebastián Hernández Sierra

Theses and Dissertations--Chemical and Materials Engineering

Nano-structured material fabrication using functionalized membranes with polyelectrolytes is a promising research field for water pollution, catalytic and mining applications. These responsive polymers react to external stimuli like temperature, pH, radiation, ionic strength or chemical composition. Such nanomaterials provide novel hybrid properties and can also be self-supported in addition to the membranes.

Polyelectrolytes (as hydrogels) have pH responsiveness. The hydrogel moieties gain or lose protons based on the pH, displaying swelling properties. These responsive materials can be exploited to synthesize metal nanoparticles in situ using their functional groups, or to immobilize other polyelectrolytes and biomolecules. Due to their properties, these …

Biopolymeric Mucin And Synthetic Polymer Analogs: Their Structure, Function And Role In Biomedical Applications, Sundar Prasanth Authimoolam, Thomas D. Dziubla

Chemical and Materials Engineering Faculty Publications

Mucin networks are viscoelastic fibrillar aggregates formed through the complex self-association of biopolymeric glycoprotein chains. The networks form a lubricious, hydrated protective shield along epithelial regions within the human body. The critical role played by mucin networks in impacting the transport properties of biofunctional molecules (e.g., biogenic molecules, probes, nanoparticles), and its effect on bioavailability are well described in the literature. An alternate perspective is provided in this paper, presenting mucin’s complex network structure, and its interdependent functional characteristics in human physiology. We highlight the recent advances that were achieved through the use of mucin in diverse areas of bioengineering …

Bioactive Poly(Beta-Amino Ester) Biomaterials For Treatment Of Infection And Oxidative Stress, Andrew L. Lakes

Theses and Dissertations--Chemical and Materials Engineering

Polymers have deep roots as drug delivery tools, and are widely used in clinical to private settings. Currently, however, numerous traditional therapies exist which may be improved through use of polymeric biomaterials. Through our work with infectious and oxidative stress disease prevention and treatment, we aimed to develop application driven, enhanced therapies utilizing new classes of polymers synthesized in-house. Applying biodegradable poly(β-amino ester) (PBAE) polymers, covalent-addition of bioactive substrates to these PBAEs avoided certain pitfalls of free-loaded and non-degradable drug delivery systems. Further, through variation of polymer ingredients and conditions, we were able to tune degradation rates, release profiles, cellular …

Synthesis Of Titania Thin Films With Controlled Mesopore Orientation: Nanostructure For Energy Conversion And Storage, Suraj R. Nagpure

Theses and Dissertations--Chemical and Materials Engineering

This dissertation addresses the synthesis mechanism of mesoporous titania thin films with 2D Hexagonal Close Packed (HCP) cylindrical nanopores by an evaporation-induced self-assembly (EISA) method with Pluronic surfactants P123 and F127 as structure directing agents, and their applications in photovoltaics and lithium ion batteries. To provide orthogonal alignment of the pores, surface modification of substrates with crosslinked surfactant has been used to provide a chemically neutral surface. GISAXS studies show not only that aging at 4°C facilitates ordered mesostructure development, but also that aging at this temperature helps to provide orthogonal orientation of the cylindrical micelles which assemble into an …

Evaporation-Induced Formation Of Well-Ordered Surface Patterns On Polymer Films, Wei Sun

Theses and Dissertations--Chemical and Materials Engineering

Various techniques of fabricating surface patterns of small scales have been widely studied due to the potential applications of surface patterns in a variety of areas. It is a challenge to fabricate well-ordered surface area efficiently and economically. Evaporation-induced surface patterning is a promising approach to fabricate well-ordered surface patterns over a large area at low cost. In this study, the evaporation-induced surface patterns with controllable geometrical characteristics have been constructed. The dewetting kinetics on deformable substrate is also investigated.

Using simple templates to control the geometry and the evaporation behavior of a droplet of volatile solvent, various gradient surface …

Effects Of Sodium Hydroxide Pretreatment On Structural Components Of Biomass, Alicia A. Modenbach, Sue E. Nokes

Biosystems and Agricultural Engineering Faculty Publications

Pretreatment is a unit operation in the conversion of biomass to valuable products that utilizes various combinations of conditions, including chemicals, heat, pressure, and time, to reduce the recalcitrance of lignocellulose. Many such pretreatments have been developed over the years, as the operating conditions can be adapted so that lignocellulose is modified in ways unique to each pretreatment. By tailoring pretreatment conditions to achieve these modifications, the types of final products produced can be controlled. The purpose of this review is to provide a consolidated source of information for sodium hydroxide effects on lignocellulose. The structural characteristics of lignocellulose and …

Development Of Cementitious Materials For Adhesion Type Applications Comprising Calcium Sulfoaluminate (Csa) Cement And Latex Polymer, Joshua V. Brien

Theses and Dissertations--Civil Engineering

The objective of this research was to develop high performing polymer modified calcium sulfoaluminate (CSA) cement materials for use in applications requiring superior adhesion characteristics. Little information is available describing interactions of CSA cement containing minor phase tri-calcium aluminate (C₃A) with commonly used admixtures. Given the scarcity of information, a basic approach for developing cementitious materials was followed. The basic approach consisted of four tasks: cement design, admixture design, polymer design and testing developed materials. The iterative, time consuming process is necessary for understanding the influence of specific constituent components on overall system behavior. Results from the cement …

Characterization Of And Controlling Morphology Of Ultra-Thin Nanocomposites, Guy C. Laine

Theses and Dissertations--Chemical and Materials Engineering

Ultrathin film nanocomposites are becoming increasingly important for specialized performance of commercial coatings. Critical challenges for ultrathin film nanocomposites include their synthesis and characterization as well as their performance properties, including surface roughness, optical properties (haze, refractive index as examples), and mechanical properties. The objective of this work is to control the surface roughness of ultrathin film nanocomposites by changing the average particle size and the particle volume fraction (loading) of monomodal particle size distributions. This work evaluated one-layer and two-layer films for their surface properties. Monodispersed colloidal silica nanoparticles were incorporated into an acrylate-based monomer system as the model …