Chemical Engineering Commons^™

Development Of Novel Polymeric Materials For Their Application In Monitoring And Remediation Of Environmental Pollutants, Rishabh Shah

Theses and Dissertations--Chemical and Materials Engineering

Remediation of environmental pollutants from water is one of the major challenges in the 21st century. Utilizing novel polymeric materials to accomplish this challenge has garnered a lot of interest in recent times. Flexibility in synthesizing as well as functionalizing makes them attractive for their application in pollutant remediation. This work is based on development and characterization of novel crosslinked polymeric as well as linear polymeric materials from biphenyl-based monomers, biphenyl based crosslinker and a temperature responsive monomer (Nisopropylacrylamide (NIPAAm)) for their application in remediation of toxic pollutants such as polychlorinated biphenyls (PCBs), polyaromatic hydrocarbons (PAHs) and iron oxide nanoparticle …

Coarse-Grained Dynamically Accurate Simulations Of Ionic Liquids At Vacuum-Interface, Tyler D. Stoffel

Theses and Dissertations--Mechanical Engineering

Ionic liquids, possessing improved properties in many areas of technical application, are excellent candidates as components in development of next-generation technology, including ultra-high energy batteries. If they are thus applied, however, extensive interfacial analysis of any selected ionic configuration will likely be required. Molecular dynamics (MD) provides an advantageous route by which this may be accomplished, but can fall short in observing some phenomena only present at larger time/length scales than it can simulate. Often times this is approached by coarse-graining (CG), with which scope of simulation can be significantly increased. However, coarse-grained MD systems are generally known to produce …

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 …

Composite Membranes Derived From Cellulose And Lignin Sulfonate For Selective Separations And Antifouling Aspects, Andrew Steven Colburn, Ronald J. Vogler, Aum Patel, Mariah Bezold, John D. Craven, Chunqing Liu, Dibakar Bhattacharyya

Chemical and Materials Engineering Faculty Publications

Cellulose-based membrane materials allow for separations in both aqueous solutions and organic solvents. The addition of nanocomposites into cellulose structure is facilitated through steric interaction and strong hydrogen bonding with the hydroxy groups present within cellulose. An ionic liquid, 1-ethyl-3-methylimidazolium acetate, was used as a solvent for microcrystalline cellulose to incorporate graphene oxide quantum dots into cellulose membranes. In this work, other composite materials such as, iron oxide nanoparticles, polyacrylic acid, and lignin sulfonate have all been uniformly incorporated into cellulose membranes utilizing ionic liquid cosolvents. Integration of iron into cellulose membranes resulted in high selectivity (> 99%) of neutral …

Effect Of Crystallization Modes In Tips-Pentacene/Insulating Polymer Blends On The Gas Sensing Properties Of Organic Field-Effect Transistors, Jung Hun Lee, Yena Seo, Yeong Don Park, John E. Anthony, Do Hun Kwak, Jung Ah Lim, Sunglim Ko, Ho Won Jang, Kilwon Cho, Wi Hyoung Lee

Center for Applied Energy Research Faculty and Staff Publications

Blending organic semiconductors with insulating polymers has been known to be an effective way to overcome the disadvantages of single-component organic semiconductors for high-performance organic field-effect transistors (OFETs). We show that when a solution processable organic semiconductor (6,13-bis(triisopropylsilylethynyl)pentacene, TIPS-pentacene) is blended with an insulating polymer (PS), morphological and structural characteristics of the blend films could be significantly influenced by the processing conditions like the spin coating time. Although vertical phase-separated structures (TIPS-pentacene-top/PS-bottom) were formed on the substrate regardless of the spin coating time, the spin time governed the growth mode of the TIPS-pentacene molecules that phase-separated and crystallized on the …

Towards The Rational Design And Application Of Polymers For Gene Therapy: Internalization And Intracellular Fate, Landon Alexander Mott

Theses and Dissertations--Chemical and Materials Engineering

Gene therapy is an approach for the treatment of acquired cancers, infectious disease, degenerative disease, and inherited genetic indications. Developments in the fields of immunotherapies and CRISPR/Cas9 genome editing are revitalizing the efforts to move gene therapy to the forefront of modern medicine. However, slow progress and poor clinical outcomes have plagued the field due to regulatory and safety concerns associated with the flagship delivery vector, the recombinant virus. Immunogenicity and poor transduction in certain cell types severely limits the utility of viruses as a delivery agent of nucleic acids. As a result, significant efforts are being made to develop …

Nanoharvesting And Delivery Of Bioactive Materials Using Engineered Silica Nanoparticles, Md Arif Khan

Theses and Dissertations--Chemical and Materials Engineering

Mesoporous silica nanoparticles (MSNPs) possess large surface areas and ample pore space that can be readily modified with specific functional groups for targeted binding of bioactive materials to be transported through cellular barriers. Engineered silica nanoparticles (ESNP) have been used extensively to deliver bio-active materials to target intracellular sites, including as non-viral vectors for nucleic acid (DNA/RNA) delivery such as for siRNA induced interference. The reverse process guided by the same principles is called “nanoharvesting”, where valuable biomolecules are carried out and separated from living and functioning organisms using nano-carriers. This dissertation focuses on ESNP design principles for both applications. …

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 …

Determining The Degree Of [001] Preferred Growth Of Ni(Oh)2 Nanoplates, Taotao Li, Ning Dang, Wanggang Zhang, Wei Liang, Fuqian Yang

Chemical and Materials Engineering Faculty Publications

Determining the degree of preferred growth of low-dimensional materials is of practical importance for the improvement of the synthesis methods and applications of low-dimensional materials. In this work, three different methods are used to analyze the degree of preferred growth of the Ni(OH)₂ nanoplates synthesized without the use of a complex anion. The results suggest that the preferred growth degree of the Ni(OH)₂ nanoplates calculated by the March parameter and the expression given by Zolotoyabko, which are based on the analysis and texture refinement of the X-ray diffraction pattern, are in good accordance with the results measured by …

Self-Cleaning Nanocomposite Membranes With Phosphorene-Based Pore Fillers For Water Treatment, Joyner Eke, Katherine Elder, Isabel Escobar

Chemical and Materials Engineering Faculty Publications

Phosphorene is a two-dimensional material exfoliated from bulk phosphorus and it possesses a band gap. Specifically, relevant to the field of membrane science, the band gap of phosphorene provides it with potential photocatalytic properties, which could be explored in making reactive membranes that can self-clean. The goal of this study was to develop an innovative and robust membrane that is able to control and reverse fouling with minimal changes in membrane performance. To this end, for the first time, membranes have been embedded with phosphorene. Membrane modification was verified by the presence of phosphorus on membranes, along with changes in …

Surface And Structural Modification Of Carbon Electrodes For Electroanalysis And Electrochemical Conversion, Yan Zhang

Theses and Dissertations--Chemistry

Electrocatalysis is key to both sensitive electrochemical sensing and efficient electrochemical energy conversion. Despite high catalytic activity, traditional metal catalysts have poor stability, low selectivity, and high cost. Metal-free, carbon-based materials are emerging as alternatives to metal-based catalysts because of their attractive features including natural abundance, environmental friendliness, high electrical conductivity, and large surface area. Altering surface functionalities and heteroatom doping are effective ways to promote catalytic performance of carbon-based catalysts. The first chapter of this dissertation focuses on developing electrode modification methods for electrochemical sensing of biomolecules. After electrochemical pretreatment, glassy carbon demonstrates impressive figures-of-merit in detecting small, redox-active …

Synergistic Interactions Of H2 And N2 With Molten Gallium In The Presence Of Plasma, Maria L. Carreon, Daniel F. Jaramillo-Cabanzo, Indira Chaudhuri, Madhu Menon, Mahendra K. Sunkara

Physics and Astronomy Faculty Publications

The present study examines the interaction of hydrogen and nitrogen plasmas with gallium in an effort to gain insights into the mechanisms behind the synergetic effect of plasma and a catalytic metal. Absorption/desorption experiments were performed, accompanied by theoretical-computational calculations. Experiments were carried out in a plasma-enhanced, Ga-packed, batch reactor and entailed monitoring the change in pressure at different temperatures. The results indicated a rapid adsorption/dissolution of the gas into the molten metal when gallium was exposed to plasma, even at a low temperature of 100 °C. The experimental observations, when hydrogen was used, indicate that gallium acts as a …

Size And Shape Distributions Of Primary Crystallites In Titania Aggregates, Eric A. Grulke, Kazuhiro Yamamoto, Kazuhiro Kumagai, Ines Häusler, Werner Österle, Erik Ortel, Vasile-Dan Hodoroaba, Scott C. Brown, Christopher Chan, Jiwen Zheng, Kenji Yamamoto, Kouji Yashiki, Nam Woong Song, Young Heon Kim, Aleksandr B Stefaniak, D. Schwegler-Berry, Victoria A. Coleman, Åsa K. Jämting, Jan Herrmann, Toru Arakawa, Woodrow W. Burchett, Joshua W. Lambert, Arnold J. Stromberg

Chemical and Materials Engineering Faculty Publications

The primary crystallite size of titania powder relates to its properties in a number of applications. Transmission electron microscopy was used in this interlaboratory comparison (ILC) to measure primary crystallite size and shape distributions for a commercial aggregated titania powder. Data of four size descriptors and two shape descriptors were evaluated across nine laboratories. Data repeatability and reproducibility was evaluated by analysis of variance. One-third of the laboratory pairs had similar size descriptor data, but 83% of the pairs had similar aspect ratio data. Scale descriptor distributions were generally unimodal and were well-described by lognormal reference models. Shape descriptor distributions …

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 …

Fast Diffusion Of Silver In Tio2 Nanotube Arrays, Wanggang Zhang, Yiming Liu, Diaoyu Zhou, Hui Wang, Wei Liang, Fuqian Yang

Chemical and Materials Engineering Faculty Publications

Using magnetron sputtering and heat treatment, Ag@TiO₂ nanotubes are prepared. The effects of heat-treatment temperature and heating time on the evolution of Ag nanofilms on the surface of TiO₂ nanotubes and microstructure of Ag nanofilms are investigated by X-ray diffraction, field emission scanning electron microscopy, and transmission electron microscopy. Ag atoms migrate mainly on the outmost surface of the TiO₂ nanotubes, and fast diffusion of Ag atoms is observed. The diffusivity for the diffusion of Ag atoms on the outmost surface of the TiO₂ nanotubes at 400 °C is 6.87 × 10⁻¹⁸ m²/s, …

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 …

Peptide-Functionalized Magnetic Nanoparticles For Cancer Therapy Applications, Anastasia K. Hauser

Theses and Dissertations--Chemical and Materials Engineering

Lung cancer is one of the leading causes of cancer deaths in the United States. Radiation and chemotherapy are conventional treatments, but they result in serious side effects and the probability of tumor recurrence remains high. Therefore, there is an increasing need to enhance the efficacy of conventional treatments. Magnetic nanoparticles have been previously studied for a variety of applications such as magnetic resonance imaging contrast agents, anemia treatment, magnetic cell sorting and magnetically mediated hyperthermia (MMH). In this work, dextran coated iron oxide nanoparticles were developed and functionalized with peptides to target the nanoparticles to either the extracellular matrix …

Biomimetic Oral Mucin From Polymer Micelle Networks, Sundar Prasanth Authimoolam

Theses and Dissertations--Chemical and Materials Engineering

Mucin networks are formed by the complexation of bottlebrush-like mucin glycoprotein with other small molecule glycoproteins. These glycoproteins create nanoscale strands that then arrange into a nanoporous mesh. These networks play an important role in ensuring surface hydration, lubricity and barrier protection. In order to understand the functional behavior in mucin networks, it is important to decouple their chemical and physical effects responsible for generating the fundamental property-function relationship. To achieve this goal, we propose to develop a synthetic biomimetic mucin using a layer-by-layer (LBL) deposition approach. In this work, a hierarchical 3-dimensional structures resembling natural mucin networks was generated …

The Critical Role Of Mechanism-Based Models For Understanding And Predicting Liposomal Drug Loading, Binding And Release Kinetics, Sweta Modi

Theses and Dissertations--Pharmacy

Liposomal delivery systems hold considerable promise for improvement of cancer therapy provided that critical formulation design criteria can be met. The main objective of the current project was to enable quality by design in the formulation of liposomal delivery systems by developing comprehensive, mechanism-based mathematical models of drug loading, binding and release kinetics that take into account not only the therapeutic requirement but the physicochemical properties of the drug, the bilayer membrane, and the intraliposomal microenvironment.

Membrane binding of the drug affects both drug loading and release from liposomes. The influence of bilayer composition and phase structure on the partitioning …

Nanoparticle Additives For Multiphase Systems: Synthesis, Formulation And Characterization, Vinod Kanniah

Theses and Dissertations--Chemical and Materials Engineering

Study on nanoparticle additives in multiphase systems (liquid, polymer) are of immense interest in developing new product applications. Critical challenges for nanoparticle additives include their synthesis, formulation and characterization. These challenges are addressed in three application areas: nanofluids for engine lubrication, ultrathin nanocomposites for optical devices, and nanoparticle size distribution characterization.

Nanoparticle additives in oligomer mixtures can be used to develop extended temperature range motor oils. A model system includes poly(α-olefin) based oligomers with a modest fraction of poly(dimethylsiloxane) oligomers along with graphite as nanoparticle additive. Partition coefficients of each oligomer are determined since the oligomer mixture phase separated at …

Nanoscale Functionalization And Characterization Of Surfaces With Hydrogel Patterns And Biomolecules, Hariharasudhan Chirra Dinakar

University of Kentucky Doctoral Dissertations

The advent of numerous tools, ease of techniques, and concepts related to nanotechnology, in combination with functionalization via simple chemistry has made gold important for various biomedical applications. In this dissertation, the development and characterization of planar gold surfaces with responsive hydrogel patterns for rapid point of care sensing and the functionalization of gold nanoparticles for drug delivery are highlighted.

Biomedical micro- and nanoscale devices that are spatially functionalized with intelligent hydrogels are typically fabricated using conventional UV-lithography. Herein, precise 3-D hydrogel patterns made up of temperature responsive crosslinked poly(N-isopropylacrylamide) over gold were synthesized. The XY control of the hydrogel …