Polymer and Organic Materials Commons^™

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 …

Effect Of Interlayers On Mechanical Properties And Interfacial Stress Transfer Of 2d Layered Graphene-Polymer Nanocompsites, Colton C. Roach

Theses and Dissertations--Mechanical and Aerospace Engineering

Graphene, a monolayer of sp²-hybridized carbon atoms arranged in a two-dimensional (2D) lattice, is one of the most important 2D nanomaterials and has attracted tremendous attentions due to its unique geometric characteristics and exceptional mechanical properties. One of the most promising applications of this 2D nanomaterial is in polymer nanocomposites, in which the ultra-stiff, ultra-thin graphene layers function as reinforcement fillers. However, two significant questions remain to be answered: (1) whether the mechanical behaviors of 2D graphene reinforced nanocomposites can be analyzed by the convention composite theory, which is developed primarily for one-dimensional (1D) fiber-type of fillers, and …

The Limits & Effects Of Draw On Properties And Morphology Of Pan-Based Precursor And The Resultant Carbon Fibers, Sarah Edrington

Theses and Dissertations--Mechanical and Aerospace Engineering

The process, structure, and property relationship of PAN fiber as a precursor to carbon fiber was studied. The limitations of stable spinning and property improvement associated with hot draw in solution spinning were found and quantified. Conditions were varied to generated precursor fiber up to the limit of draw, from which actual samples were collected for thermal conversion to carbon fiber. Samples of PAN and subsequent carbon fiber were characterized using tensile testing and x-ray analysis. The effects of draw on modulus and break stress, as well as the orientation of the crystalline structure of both parent precursor and resultant …

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 …

Spray Printing Of Organic Semiconducting Single Crystals, Grigorios-Panagiotis Rigas, Marcia M. Payne, John E. Anthony, Peter N. Horton, Fernando A. Castro, Maxim Shkunov

Chemistry Faculty Publications

Single-crystal semiconductors have been at the forefront of scientific interest for more than 70 years, serving as the backbone of electronic devices. Inorganic single crystals are typically grown from a melt using time-consuming and energy-intensive processes. Organic semiconductor single crystals, however, can be grown using solution-based methods at room temperature in air, opening up the possibility of large-scale production of inexpensive electronics targeting applications ranging from field-effect transistors and light-emitting diodes to medical X-ray detectors. Here we demonstrate a low-cost, scalable spray-printing process to fabricate high-quality organic single crystals, based on various semiconducting small molecules on virtually any substrate by …

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 …

Strain Effects On The Work Function Of An Organic Semiconductor, Yanfei Wu, Annabel R. Chew, Geoffrey A. Rojas, Gjergji Sini, Greg Haugstad, Alex Belianinov, Sergei V. Kalinin, Hong Li, Chad Risko, Jean-Luc Brédas, Alberto Salleo, C. Daniel Frisbie

Chemistry Faculty Publications

Establishing fundamental relationships between strain and work function (WF) in organic semiconductors is important not only for understanding electrical properties of organic thin films, which are subject to both intrinsic and extrinsic strains, but also for developing flexible electronic devices. Here we investigate tensile and compressive strain effects on the WF of rubrene single crystals. Mechanical strain induced by thermal expansion mismatch between the substrate and rubrene is quantified by X-ray diffraction. The corresponding WF change is measured by scanning Kelvin probe microscopy. The WF of rubrene increases (decreases) significantly with in-plane tensile (compressive) strain, which agrees qualitatively with density …

Evaluation Of Flocculation, Sedimentation, And Filtration For Dewatering Of Algal Biomass, Nicholas A. Rhea

Theses and Dissertations--Biosystems and Agricultural Engineering

Algae can be used as a feedstock for agricultural fertilizers, livestock/poultry feeds, anaerobic digestion, and biofuel production. Regardless of the end product, water removal is necessary and difficult to do cost effectively. For each product the requirements for moisture content (or solids content) vary, such that a desirable water removal strategy would need to be adaptable to varying levels of water removal. Flocculation, with sedimentation and drying was evaluated as a possible strategy for algae dewatering. Anionic and nonionic flocculants are known to be ineffective at flocculating algal culture, which was confirmed for this case by electro-osmotic flow testing of …

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 …

First-Principles Studies Of Structure-Property Relationships: Enabling Design Of Functional Materials, Qunfei Zhou

Theses and Dissertations--Chemical and Materials Engineering

First-principles calculations based on quantum mechanics have been proved to be powerful for accurately regenerating experimental results, uncovering underlying myths of experimental phenomena, and accelerating the design of innovative materials. This work has been motivated by the demand to design next-generation thermionic emitting cathodes and techniques to allow for synthesis of photo-responsive polymers on complex surfaces with controlled thickness and patterns. For Os-coated tungsten thermionic dispenser cathodes, we used first-principles methods to explore the bulk and surface properties of W-Os alloys in order to explain the previously observed experimental phenomena that thermionic emission varies significantly with W-Os alloy composition. Meanwhile, …

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 …

Magnesium-Titanium Alloys For Biomedical Applications, Ilona Hoffmann

Theses and Dissertations--Chemical and Materials Engineering

Magnesium has been identified as a promising biodegradable implant material because it does not cause systemic toxicity and can reduce stress shielding. However, it corrodes too quickly in the body. Titanium, which is already used ubiquitously for implants, was chosen as the alloying element because of its proven biocompatibility and corrosion resistance in physiological environments. Thus, alloying magnesium with titanium is expected to improve the corrosion resistance of magnesium.

Mg-Ti alloys with a titanium content ranging from 5 to 35 at.-% were successfully synthesized by mechanical alloying. Spark plasma sintering was identified as a processing route to consolidate the alloy …

Addressing Public Health Risks Of Persistent Pollutants Through Nutritional Modulation And Biomimetic Nanocomposite Remediation Platforms, Bradley J. Newsome

Theses and Dissertations--Chemistry

Due to their relative chemical stability and ubiquity in the environment, chlorinated organic contaminants such as polychlorinated biphenyls (PCBs) pose significant health risks and enduring remediation challenges. Engineered nanoparticles (NPs) provide a novel platform for sensing/remediation of these toxicants, in addition to the growing use of NPs in many industrial and biomedical applications, but there remains concern for their potential long-term health effects. Research highlighted herein also represents a transdisciplinary approach to address human health challenges associated with exposure to PCBs and NPs. The objectives of this dissertation research are two-fold, 1) to develop effective methods for capture/sensing and remediation …

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 …

Influence Of Surface Modification On Properties And Applications Of Complex Engineered Nanoparticles, Binghui Wang

Theses and Dissertations--Chemical and Materials Engineering

Complex engineered nanoparticles (CENPs) are being used on various applications. Their properties are different from those of neat nanoparticles. The dissertation explores these differences from four aspects: 1) Modify carbon nanomaterials’ inert surfaces and investigate the effect on thermal and rheological behavior of their dispersions; 2) Generate self-assembly bi-layer structure of oxide nanoparticles via surface modification; 3) Study interaction between lysozyme and different surface-charged ceria nanoparticles; 4) Investigate the biodistribution and transformations of CENPs in biological media.

An environment-friendly surface modification was developed to modify surfaces of carbon nanomaterials for increasing their affinity to non-polar fluid. It can offset formation …

Sorption Of Chlorinated Organic Compounds By Sedimentary Rocks, Paul M. Mcginley, S. Kesaraju, Ronald D. Gruzesky

KWRRI Research Reports

The sorption of dichlorobenzene and trichlorobenzene on carbonate and shale rocks collected in Kentucky demonstrate that rock organic matter content is a good indicator of sorptive reactivity in rock systems. Although this is similar to soil systems, significant differences between sorption in rock and soil systems exist. Sorption isotherms on these rocks are nonlinear and sorption can be an order of magnitude higher than predicted using correlations from soils and their organic matter content. This sorption reaction could lead to significant concentration tailing during contaminant cleanup. Experimental elution of trichloroethylene from rock filled columns verified that cleanup times might be …

Use Of High-Energy Radiation For Degradation Of Environmental Pollutants, Robert D. Guthrie, Manjiri Patwardhan

KWRRI Research Reports

The purpose of this project was to explore the advantages and/or limitations of high-energy radiation treatment as a method for degrading organic pollutants, particularly aryl halides, in an aqueous medium. We have done analyses of ⁶⁰Co-irradiated samples and kinetic studies using pulsed electron beams. For aryl halides containing no more than two fused rings, the main products detected are those of simple halogen replacement by hydrogen, although the amount of aryl halide destroyed was always greater than the total amount of products detected. To accomplish halogen replacement by H, the reaction solvent may not be pure water but must …

Chemistry Of The Oxidant, Ferrate, Its Interaction With Specific Organics Found In Waste Water, Donald H. Williams, J. T. Riley

KWRRI Research Reports

It became obvious during this investigation that while much work has been done with ferrate (VI) chemistry, discrepancies existed in the literature and very little attention had been given possible engineering uses. This work attempted to fulfill these two needs in an exploratory manner.

The preparative techniques were reviewed and mechanical improvements made in one which allowed improved yields. Essentially what was done was to enlarge and improve the filtering technique of the product and use cooler temperatures throughout the preparation. This greatly shortened the time required. Then it was learned that the addition of ethyl alcohol to the final …