Engineering Commons^™

Production And Applications Of Formaldehyde-Free Phenolic Resins Using 5-Hydroxymethylfurfural Derived From Glucose In-Situ, Yongsheng Zhang

Electronic Thesis and Dissertation Repository

The phenol-formaldehyde (PF) resin manufacturing industry is facing a growing challenge with respect to concerns over human health, due to the use of carcinogenic formaldehyde and sustainability due to the use of petroleum-based phenol in PF resin manufacture. Glucose and its derivative, 5-hydroxymethylfurfural (5-HMF), have proven to be potential substitutes for formaldehyde in the synthesis of phenolic novolac resins.

This thesis investigated a number of glucose and 5-HMF resin systems including the curing of phenol-glucose novolac resin (PG) with a bis-phenol-A type epoxy. The curing process was modeled according to the Sestak-Berggren equation (S, B) using Málek methods. This was …

The Development Of A Laminated Copolyester Electric Guitar, Addison S. Karnes

Electronic Theses and Dissertations

This thesis is an investigation of the fabrication and assembly methodologies employed in the development of a proof-of-principle prototype electric guitar composed of laminated copolyester. The objective of the project was to develop the processes and procedures to create an optimized physical and visual bond between layers to minimize vibratory dissipation, thus maximizing sustain. A high speed CNC router, abrasive waterjet, laser engraver-cutter, as well as various manual fabrication and assembly methods were investigated in the construction of the guitar prototypes. The lamination processes explored include low-temperature, heat-assisted pressure bonding, solvent and chemical welding, and contact adhesives. The project concluded …

Designing Magnetically Responsive Ultrafiltration Membranes, Robert William Dong

Graduate Theses and Dissertations

Ultrafiltration (UF) membranes developed out of a need for protein separation processes. Currently, they are used in a variety of industries ranging from food manufacturing to pharmaceuticals for two main purposes: concentration, separation, and buffer exchange. UF membrane processes in product streams undergo frequent use and like all membrane processes experience a gradual decline in performance due to fouling phenomena both irreversible and reversible. Ultimately, performance declines to a point where the UF membrane needs to be replaced. Frequent replacement of UF membranes is detrimental to major industries that require high product throughput using UF processes. Thus, it is important …

Thermally Responsive Polymer Electrolytes For Inherently Safe Electrochemical Energy Storage, Jesse Kelly

All Dissertations

Electrochemical double layer capacitors (EDLCs), supercapacitors and Li-ion batteries have emerged as premier candidates to meet the rising demands in energy storage; however, such systems are limited by thermal hazards, thermal runaway, fires and explosions, all of which become increasingly more dangerous in large-format devices. To prevent such scenarios, thermally-responsive polymer electrolytes (RPEs) that alter properties in electrochemical energy storage devices were designed and tested. These RPEs will be used to limit or halt device operation when temperatures increase beyond a predetermined threshold, therefore limiting further heating. The development of these responsive systems will offer an inherent safety mechanism in …

Microanalysis Of Polymer Chain Diffusion In Heat Seals, Russell Cooper

All Theses

Heat sealing is an integral method for the closure and protection of packaging. Previous work has shown that seal strength is developed by the interdiffusion of polymer chains within heat seals. Heat seals were made between two dissimilar materials. Poly(ethylene-co-acrylic acid) (EAA) was heat sealed to ionomer. Diffusion within the EAA-ionomer heat seals was estimated. The diffusion estimates were then related to resulting seal strength in the EAA-ionomer sealant system. Heated tooling sealing was utilized to make heat seals at 40 psi (275.79 kPa), 0.5 seconds, and a range of temperatures between 180˚F (82.22˚C) and 300˚F (148.89˚C). Scanning electron microscopy …

Analytical And Computational Modeling Of Membrane Nanotubes, Sina Mirzaeifard

Masters Theses

This thesis investigates the interplay between cell membranes and the actin cytoskeleton in cellular structures known as membrane nanotubes. Membrane nanotubes are slender membrane structures that physically connect cells over long distances, and experiments suggest that they play a role in transferring material and information between cells. Disrupting the actin cytoskeleton disrupts membrane nanotubes. Although recent studies have revealed insight into the physical properties and functions of membrane-actin systems, further research is needed to understand their behavior in biological contexts. Membrane nanotubes provide a novel system with which to investigate interactions between the cell membrane and actin.

In this thesis, …

Synthesis And Characterization Of Chemically Functionalized Shape Memory Nanofoams For Unattended Sensing Applications, Anna Paola Soliani

All Dissertations

The work in this dissertation is devoted to the synthesis and characterization of novel materials for off-line unattended sensing: shape-memory grafted nanofoams. The fabrication process and characterization of highly efficient, polymeric nanosensor element with the ability to selectively detect analytes and retain memory of specific exposure events is reported. These shape memory nanofoams could potentially act as efficient and highly sensitive coatings for evanescent waveguide-based optical monitoring systems. On exposure to specific analytes, the polymeric coatings locally change their internal structure irreversibly at the nanolevel, affecting the local optical properties such as refractive index. Currently, enrichment polymer layers (EPLs) are …

Low Molecular Weight Glucosamine/L-Lactide Copolymers As Potential Carriers For The Development Of A Sustained Rifampicin Release System: Mycobacterium Smegmatis As A Tuberculosis Model, Jorge Ragusa

Department of Chemical and Biomolecular Engineering: Theses and Student Research

Tuberculosis, a highly contagious disease, ranks as the second leading cause of death from an infectious disease, and remains a major global health problem. In 2013, 9 million new cases were diagnosed and 1.5 million people died worldwide from tuberculosis. This dissertation aims at developing a new, ultrafine particle-based efficient antibiotic delivery system for the treatment of tuberculosis. The carrier material to make the rifampicin (RIF)-loaded particles is a low molecular weight star-shaped polymer produced from glucosamine (molecular core building unit) and L-lactide (GluN-LLA). Stable particles with a very high 50% drug loading capacity were made via electrohydrodynamic atomization. Prolonged …

Evaluating Effects Of Molecular Heterogeneity On The Non-Linear Mechanical Behavior Of Epoxy Networks, Zhan Hang Yang

Doctoral Dissertations

This thesis describes synthetic and processing strategies to formulate epoxies resins with molecular heterogeneity to achieve enhanced engineering properties. The network heterogeneities include chemical differences in stiffness and crosslink density, as well as mechanical difference in baseline energy state. The focus is to understand the fundamental structure-process-property relationships in these unusual network polymers, especially the post-yield responses and fracture toughness. The main characterization techniques to probe the complex network architectures are dynamic mechanical spectroscopy and compression tests. Ductility and governing parameters are also proposed to describe the relationships between molecular structures and physical properties. Three different staged fabrication strategies are …

Structure Of Nearly Ideal And Multi-Component Polymeric Biomaterials, Erika Saffer

Doctoral Dissertations

Hydrogels have long been considered ideal candidates for biomaterial and tissue engineering applications due to their many desirable properties, such as high water content and tunable gelation conditions. Although these materials have undergone extensive research and development, some mechanical and physical properties are still difficult to achieve. The reason for this is often related to the structure of the hydrogel network. Understanding how network structures are influenced by changes in formulation parameters (i.e. polymer molecular weight, initial polymer concentration, ratio of hydrophilic to hydrophobic polymer), and correlating these results to known mechanical and physical properties would yield well characterized systems …

Humic Substances-Based Polymer System, Gerard R. Thiel

Patents (University of Northern Iowa)

A system for use in forming polymer compositions, including as a replacement for phenolic based resin systems, for instance, in preparing foundry molds. In a preferred embodiment, the system includes the use of a) a polyermizable hydroxyl-containing component comprising a humic substance (as can be provided by lignite), b) an isocyanate component, and c) a catalyst, and preferably amine catalyst, component adapted to catalyze the polymerization of a) and b). The system is optionally used as binder system in the presence of a filler, such as, in combination with a foundry aggregate such as sand. A polymer system of this …

Laser-Assisted Surface Modification Of Hybrid Hydrogels To Prevent Bacterial Contamination And Protein Fouling, Guobang Huang

Electronic Thesis and Dissertation Repository

Silicone hydrogels have been extensively studied in the fields of contact lenses, tissue engineering, and drug delivery due to their good biocompatibility, high oxygen permeability, and proper light transmission. However, their applications in biomedical devices are limited by protein adsorption and bacterial contamination because of the hydrophobic surface of silicone, which will cause more irreversible protein adsorption. Several physical methods can be applied to create a hydrophilic surface on hydrogels, such as spin coating, physical vapor deposition, dip coating, drop casting, etc. Compared to the conventional methods, the matrix assisted pulsed laser evaporation (MAPLE) is suitable to produce biopolymer/polymer film …

Polymer-Based Thermoelectric Devices, Stuart W. Hilsmier, Edward P. Tomlinson, Bryan Boudouris

The Summer Undergraduate Research Fellowship (SURF) Symposium

Currently, over 50% of all energy generated in the US is lost as waste heat, and thermoelectric generators offer a promising means to recoup some of this energy, if their efficiency is improved. While organic thermoelectric materials lack the efficiency of their inorganic counterparts, they are composed of highly abundant resources and have low temperature processing conditions. Recently, a new class of redox-active polymers, radical polymers, has exhibited high electrical conductivity in an entirely amorphous medium. In addition, these radical polymers have a simple synthetic scheme and can be highly tunable to provide desired electrical properties. In this study, the …

Radical Polymers As Anodic Charge Extraction Layers In Small Molecule Organic Photovoltaic Devices, Krystopher S. Jochem, Aditya G. Baradwaj, Bryan W. Boudouris

The Summer Undergraduate Research Fellowship (SURF) Symposium

Organic photovoltaic (OPV) devices based on the copper (II) phthalocyanine(CuPc)/ fullerene(C₆₀) system are an innovative photovoltaic technology optimal for situations requiring low-cost, transparent, and flexible devices. Furthermore, the high degree of reproducibility of this system allows for the ready study of new OPV technologies. Here, we have used this system to elucidate systematic structure-property-performance relationships for a new OPV anode modifier. The addition of interfacial modifier materials between the organic CuPc/C₆₀ layers and the metallic anode drastically can improve efficiency. Radical polymers are a class of polymers with aliphatic backbones and pendent stabilized radical groups. Here, we …

Composition Dependence Of The Flory-Huggins Interaction Parameter In Polymer Blends: Structural And Thermodynamic Calculations, Travis H. Russell

Doctoral Dissertations

Flory-Huggins Theory has been the basis for understanding polymer solvent and blended polymer thermodynamics for much of the last 60 years. Within this theory, a parameter (χ) [chi] was included to quantify the enthalpic energy of dispersion between distinct components. Thin film self-assembly of polymer melts and block copolymers depends critically on this parameter, and in application, χ has generally been assumed to be independent of the concentrations of the individual components of the system. However, Small-Angle Neutron Scattering data on isotopic polymer blends, such as polyethylene and deuterated polyethylene, have shown a roughly parabolic concentration dependency for …

Fluorine Containing Uv-Curable Materials For Advanced Transport Applications, James Thomas Goetz

Dissertations

The characterization of structure, thermal, gas transport, and free volume properties of two unique UV cured polymeric systems are studied and reported. In the initial pursuit of waterproof high water vapor transport membranes, it became apparent that the UV curing of fluorinated materials yielded routes to develop unique materials that fundamentally challenge conventional models for free volume and light gas transport behavior. UV-curing provides a means to rapidly “lock-in” morphologies that are accessible in the small molecule, monomer phase but rapidly become kinetically inaccessible when constraints such as covalent bonding and cross linking limit motion in the polymer system. This …

Improved Efficiency Organic Photovoltaic Cells Through Morphology Control And Process Modification, Qi Wu

Dissertations

Organic photovoltaic (OPV) cells have drawn great attention due to the potential to produce flexible, light weight, affordable solar cells using polymer organic photovoltaic materials; however, the current power conversion efficiency achieved for these systems is too low for widespread implementation of the technology. Morphology and phase separation are key factors determining the performance of organic photovoltaic cells. Precise control of the size and distribution of the phase-separated photoactive domains is necessary for optimum photon-electron conversion. Polyhedral oligomeric silsesquioxane (POSS) nanostructered chemicals have the potential to provide enhanced control of morphology, crystallinity, and phase dispersion in polymeric blend systems. In …

Fundamental Investigations Of Clay/Polymer Nanocomposites And Applications In Co-Extruded Microlayered Systems, Jeremy John Decker

Dissertations

The second and fourth generations of hydroxylated dendritic polyesters (HBP2, HBP4) were combined with unmodified sodium montmorillonite clay (Na+MMT) in water to generate a broad range of polymer clay nanocomposites from 0 to 100% wt/wt Na+MMT. X-ray diffraction (XRD) and transmission electron microscopy (TEM) were used to investigate intercalation states of the clay galleries. It was shown that interlayer spacings were independent of generation number and changed over the composition range from 0.5 nm to 3.5 nm in 0.5 nm increments that corresponded to a flattened HBP conformation within the clay tactoids.

The HBP4/Na+MMT systems were investigated to study the …

High-Productivity Membrane Adsorbers: Polymer Surface-Modification Studies For Ion-Exchange And Affinity Bioseparations, Heather Chenette

All Dissertations

This Dissertation centers on the surface-modification of macroporous membranes to make them selective adsorbers for different proteins, and the analysis of the performance of these membranes relative to existing technology. Traditional chromatographic separations for the isolation and purification of proteins implement a column packed with resin beads or gel media that contain specific binding ligands on their exposed surface area. The productivity of this process is balanced by the effective use of the binding sites within the column and the speed at which the separation can take place, in addition to the need to maintain sufficient protein purity and bioactivity. …

A Soft Condensed Matter Approach Towards Mathematical Modelling Of Mass Transport And Swelling In Food Grains, Michael Chapwanya, N. Misra

Articles

Soft condensed matter (SCM) physics has recently gained importance for a large class of engineering materials. The treatment of food materials from a soft matter perspective, however, is only at the surface and is gaining importance for understanding the complex phenomena and structure of foods. In this work, we present a theoretical treatment of navy beans from a SCM perspective to describe the hydration kinetics. We solve the transport equations within a porous matrix and employ the Flory–Huggin’s equation for polymer–solvent mixture to balance the osmotic pressure. The swelling of the legume seed is modelled as a moving boundary with …

Interfacial Interactions Between Carbon Nanoparticles And Conjugated Polymers, Yanqi Luo

Master's Theses

Conjugated polymer based electronics, a type of flexible electronic devices, can be produced from solution by traditional printing and coating processes in a roll-to-roll format such as papers and graphic films. This shows great promise for the emerging energy generation and conversion. The device performance of polymer electronics is largely dependent of crystalline structures and morphology of photoactive layers. However, the solution crystallization kinetics of conjugated polymers in the presence of electron acceptor nanoparticles has not been fully understood yet. In this study, solution crystallization kinetics of poly (3-hexylthiophene) in the presence of carbon nanotubes and graphene oxide has been …

Synthesis, Properties, And Applications Of Carboxylic Acid Functionalized Polyisobutylene, Inderpreet Sran

Electronic Thesis and Dissertation Repository

Polyisobutylene (PIB) and its copolymers are used in a wide range of commercial products owing to their high chemical stability, impermeability, elasticity, and biocompatibility. In this thesis, linear and arborescent PIB containing small percentages of isoprene (IP) were functionalized to provide different derivatives and their physical and biological properties were studied.

A Molecular Dynamics Simulation Of The Stability-Limited Growth Mechanism Of Peptide-Mediated Gold-Nanoparticle Synthesis, Jing Yu, Matthew Becker, Gustavo Carri

Gustavo A. Carri

The bindingof a 12-residue peptide to a Au {111} surface and nanoparticles with different sizes result in various equilibrium structures and stabilities due to the surface morphology. The equilibrium structures are represented by the distance of peptide atoms to Au surface and the stabilities of peptide residues are represented by the average change of dihedral angles.

Opto-Electronic Devices With Nanoparticles And Their Assemblies, Chieu Van Nguyen

Department of Chemical and Biomolecular Engineering: Theses and Student Research

Nanotechnology is a fast growing field; engineering matters at the nano-meter scale. A key nanomaterial is nanoparticles (NPs). These sub-wavelength (< 100nm) particles provide tremendous possibilities due to their unique electrical, optical, and mechanical properties. Plethora of NPs with various chemical composition, size and shape has been synthesized. Clever designs of sub-wavelength structures enable observation of unusual properties of materials, and have led to new areas of research such as metamaterials. This dissertation describes two self-assemblies of gold nanoparticles, leading to an ultra-soft thin film and multi-functional single electron device at room temperature. First, the layer-by-layer self-assembly of 10nm Au nanoparticles and polyelectrolytes is shown to behave like a cellular-foam with modulus below 100 kPa. As a result, the composite thin film (~ 100nm) is 5 orders of magnitude softer than an equally thin typical polymer film. The thin film can be compressed reversibly to 60% strain. The extraordinarily low modulus and high compressibility are advantageous in pressure sensing applications. The unique mechanical properties of the composite film lead to development of an ultra-sensitive tactile imaging device capable of screening for breast cancer. On par with human finger sensitivity, the tactile device can detect a 5mm imbedded object up to 20mm below the surface with low background noise. The second device is based on a one-dimensional (1-D) self-directed self-assembly of Au NPs mediated by dielectric materials. Depending on the coverage density of the Au NPs assembly deposited on the device, electronic emission was observed at ultra-low bias of 40V, leading to low-power plasma generation in air at atmospheric pressure. Light emitted from the plasma is apparent to the naked eyes. Similarly, 1-D self-assembly of Au NPs mediated by iron oxide was fabricated and exhibits ferro-magnetic behavior. The multi-functional 1-D self-assembly of Au NPs has great potential in modern electronics such as solid state lighting, plasma-based nanoelectronics, and memory devices.

Adviser: Ravi F. Saraf

Mechanisms Of Amine-Catalyzed Organosilicate Hydrolysis At Circum-Neutral Ph, Nita Sahai

Nita Sahai

Mono- and polyamines can catalyze the hydrolysis and condensation of organosilicate starting materials in biomimetic silica synthesis pathways at circum-neutral pHs and room temperature. Our study is focused on understanding the mechanistic role of amines in catalyzing the hydrolysis process that precedes condensation. We have conducted (29)Si NMR experimental studies over a range of temperature and pHs for the hydrolysis rates of trimethylethoxysilane (TMES), a model compound with only one hydrolyzable bond, combined with quantum mechanical hybrid density functional theory calculations of putative intermediate and transition-state structures for TMES and tetramethyl orthosilicate (TMOS). Comparison of calculated energies with experimentally determined …

Effects Of Pseudowollastonite (Casio3) Bioceramic On In Vitro Activity Of Human Mesenchymal Stem Cells, Nita Sahai

Nita Sahai

We report the effects of two pseudowollastonite (beta-CaSiO(3)) substrates on the attachment, viability, proliferation and osteogenic differentiation of human mesenchymal stem cells (hMSCs), and provide detailed mechanistic links of surface texture, soluble factors and culture media to cell activities. Cell attachment and viability were lower for psWf (fine-grained, roughness 0.74 microm) than for psWc (coarse-grained, roughness 1.25 microm) surface, and were ascribed to the greater specific area of the finer psWf particles resulting in higher release rate of Si, which is cytotoxic at high levels. Interestingly, proliferation was greater on psWf. Osteogenic differentiation occurred on both surfaces, indicated by calcium …

Modeling Apatite Nucleation In The Human Body And In The Geochemical Environment, Nita Sahai

Nita Sahai

No abstract provided.

Role Of Oxide Surface Chemistry And Phospholipid Phase On Adsorption And Self-Assembly: Isotherms And Atomic Force Microscopy, Nita Sahai

Nita Sahai

We have examined the effects of metal oxide surface chemistry and lipid phase on phospholipid adsorption affinity and self-assembly. Adsorption isotherms of ditridecanoylphosphocholine (DTPC) at 40 °C and pH 7.2 on quartz (α-SiO2), rutile (α-TiO2), and corundum (α-Al2O3) particle suspensions indicated oxide-dependent adsorption affinity that decreased as rutile > corundum quartz at low concentrations and corundum > rutile quartz at higher concentrations. Significantly, atomic force microscopy of DTPC and dipalmitoylphosphocholine (DPPC) at high concentration on planar oxide surfaces at 25 °C in liquid-crystal and gel phases, respectively, also showed oxide-specific adsorption. Multiple bilayers formed on corundum (100), indicating greater coverage compared to …

Nanominerals, Mineral Nanoparticles, And Earth Systems, Nita Sahai

Nita Sahai

Minerals are more complex than previously thought because of the discovery that their chemical properties vary as a function of particle size when smaller, in at least one dimension, than a few nanometers, to perhaps as much as several tens of nanometers. These variations are most likely due, at least in part, to differences in surface and near-surface atomic structure, as well as crystal shape and surface topography as a function of size in this smallest of size regimes. It has now been established that these variations may make a difference in important geochemical and biogeochemical reactions and kinetics. This …

Oxide-Dependent Adsorption Of A Model Membrane Phospholipid, Dipalmitoylphosphatidylcholine: Bulk Adsorption Isotherms, Nita Sahai

Nita Sahai

The importance of substrate chemistry and structure on supported phospholipid bilayer design and functionality is only recently being recognized. Our goal is to investigate systematically the substrate-dependence of phospholipid adsorption with an emphasis on oxide surface chemistry and to determine the dominant controlling forces. We obtained bulk adsorption isotherms at 55 °C for dipalmitoylphosphatidylcholine (DPPC) at pH values of 5.0, 7.2, and 9.0 and at two ionic strengths with and without Ca2+, on quartz (α-SiO2), rutile (α-TiO2), and corundum (α-Al2O3), which represent a wide a range of points of zero charge (PZC). Adsorption was strongly oxide- and pH-dependent. At pH …