Engineering Commons^™

Towards Completely Automated Glycan Synthesis, Matteo Panza

Dissertations

Carbohydrates are ubiquitous both in nature as biologically active compounds and in medicine as pharmaceuticals. Although there has been continued interest in the synthesis of carbohydrates, chemical methods require specialized knowledge and hence remain cumbersome. The need for development of rapid, efficient and operationally simple procedures has come to the fore. This dissertation focuses on the development of a fully automated platform that will enable both experts and non-specialists to perform the synthesis of glycans. Existing automated methods for the synthesis of oligosaccharides are highly sophisticated, operationally complex, and require significant user know-how. By contrast, high performance liquid chromatography (HPLC) …

Decorative Articles Based On Polymeric Materials, Yaser M. Asal Mr., M. A. Radwan, Hany A. Elazab Dr, Bassant Hussein, Mohamed A. Sadek

Chemical Engineering

The aim of the research is to create decorative articles based on polymeric materials, study the effects of fillers and the type of moulds that it can cope with the exothermic reaction nature of resin to create a scientific background on the usage of the resins in daily life products. The polymeric materials that will be concentrated on are the unsaturated polyester resins and epoxy resins. The unsaturated polyester is of many types and chemical constituents, the used experimentally is a general-purpose type and the epoxy also have different types and the used is a commercially 3D floor coating type. …

Thermo-Oxidative Degradation Of Hdpe Geomembranes: Effect Of Phenolic Antioxidant And Hindered Amine Light Stabilizer Concentrations, Yasin Kocak

USF Tampa Graduate Theses and Dissertations

High density polyethylene (HDPE) geomembrane is most common geomembrane which is mainly used for civil engineering applications. However, HDPE geomembrane loses its properties under oxidative degradation progress. This study aims to assess geomembranes which have different percentage of phenolic antioxidant and hindered amine light stabilizer (HALS) with under the six months of the thermal-oxidative degradation. The interactions between phenolic antioxidant, HALS and carbon black can affect the mechanical, physical and chemical properties. To monitor these properties, Differential Scanning Calorimetry (DSC), Fourier-transform Infrared Spectroscopy (FTIR), Thermogravimetric Analysis (TGA), Scanning Electron Microscopy coupled with Energy Dispersive X-ray spectroscopy (SEM/EDX), Melt Index tests, …

Designing Ion-Containing Polymers With Controlled Structure And Dynamics, Joshua Enokida

Doctoral Dissertations

Ion-containing polymers are a unique class of materials for which strong electrostatic interactions dictate physical properties. By altering molecular parameters, such as the backbone chemical structure, the ion content, and the ion-pair identity, the structure and dynamics of these polymers can be altered. Further investigation of the molecular parameters that govern their structure-property relationships is critical for the future development of these polymeric materials. Particularly, the incorporation of ammonium-based counterions into these polymers offers a facile method to tune their electrostatic interactions and hydrophobicity. Applying this concept, a bulky dimethyloctylammonium (DMOA) counterion was used to modify the organic solubility of …

Progress Toward Durable Icephobic Materials, Matthew J. Coady

Electronic Thesis and Dissertation Repository

Ice accumulation is a major engineering challenge in many fields including aerospace, power generation, transportation, and infrastructure. A variety of solutions are being researched to address this challenge. Perhaps the most promising method of combating ice accumulation is by applying coatings with low values of interfacial ice adhesion strength, τ_ice. Icephobic materials are those with ice adhesion below 100 kPa, and it has been shown that passive delamination can occur on surfaces with τ_ice below 20 kPa. While various low adhesion surfaces have been prepared, durability concerns pervade applications where surfaces experience repeated icing or freeze-thaw cycles, …

Pre-Methylation Of Lignin To Improve Storage Stability Of Oil Produced By Solvent Liquefaction, Jae-Young Kim, Parinaz Hafezi-Sefat, Sarah D. Cady, Ryan G. Smith, Robert C. Brown

Sarah Cady

In this study, we methylated hydroxyl groups (phenolic hydroxyl: Phe-OH and aliphatic hydroxyl: Aliph-OH) in soda lignin (SL) prior to solvent liquefaction to improve storage stability of the resulting oil. We investigated two methylating reagents, dimethyl sulfate (DMS) and dimethyl carbonate (DMC), for selective Phe-OH and total hydroxyl group (Phe-OH and Aliph-OH) blocking. Samples of SL, DMS-SL, and DMC-SL were depolymerized into oils under supercritical ethanol (350 °C). Both methylated lignins produced higher amounts of oils and smaller amounts of char compared to untreated SL due to suppressed charring reactions. Oil produced from SL had relatively higher functional group contents …

Self-Assembly Of Conducting Polymer Nano- And Microstructures For Energy Storage, Luciano Matteo Santino

Arts & Sciences Electronic Theses and Dissertations

Plastics are materials composed of many long chains of molecules with repeating subunits; strong interactions between neighboring molecules lead to the material used throughout the world. Plastics are commonly thought to be insulating, in stark contrast to the conductivity of metals. However, certain polymer structures were discovered to exhibit semiconducting properties, the subject of the Nobel Prize in Chemistry in 2000. Conducting polymers have a unique molecular structure with an electronically conjugated backbone, allowing electrons to freely travel both across the chain and in between chains. This work focuses on controlling the kinetics of the reaction between the vapors of …

Modification And Optimization Of Conducting Polymer-Modified, Redox-Magnetohydrodynamics (R-Mhd) Pumping For Enhanced And Sustained Microfluidics Applications, Md Foysal Zahid Khan

Graduate Theses and Dissertations

In this work, a novel microfluidic pumping approach, redox-magnetohydrodynamics (R-MHD) has improved by materials and device optimization to use in lab-on-a-chip applications. In R-MHD, magnetic flux (B) and ionic current density (j) interacts to generate body force (FB) in between active electrodes, according to the equation FB = j×B. This unique fluid pumping approach is scalable, tunable, generates flat flow profile, and does not require any channels or valves. Pumping performance, such as speed scales with the ionic current density (j) and duration depends on the total charge (Q). The ionic current density (j) results from the conversion of electronic …

Double-Network Materials Via Frontal Polymerization & Supercritical Co2 Processing, Matthew Joseph Lampe

Doctoral Dissertations

This dissertation presents work focused on producing materials in non-equilibrium states by taking advantage of novel processing techniques. First, epoxy-based resins which can undergo radically promoted, cationic, thermal, frontal polymerization are investigated for their potential use as adhesives. These resins are found to be capable of sustaining propagating polymerization fronts between several different substrate materials, resulting in high levels of adhesion in some cases. In addition, a similar frontal resin was developed that can undergo sequential gelation and frontal polymerization. The gels are formed by radically crosslinking acrylate monomers within the epoxy resin. These gels can then be manipulated, and …

Non-Einstein Viscosity Phenomenon Of Acrylonitrile–Butadiene–Styrene Composites Containing Lignin–Polycaprolactone Particulates Highly Dispersed By High-Shear Stress, Sing-Hoon Kim, Kisuk Choi, Kyouk Ryeol Choi, Taesung Kim, Jonghwan Suhr, Kwang Jin Kim, Hyoung Jin Choi, Jae-Do Nam

Mechanical Engineering Faculty Research

Lignin powder was modified via ring-opening polymerization of caprolactone to form a lignin–polycaprolactone (LPCL) particulate. The LPCL particulates were mixed with an acrylonitrile–butadiene–styrene (ABS) matrix at an extremely high rotational speed of up to 3000 rpm, which was achieved by a closed-loop screw mixer and in-line melt extruder. Using this high-shear extruding mixer, the LPCL particulate size was controlled in the range of 3395 nm (conventional twin-screw extrusion) down to 638 nm (high-shear mixer of 3000 rpm) by altering the mixing speed and time. The resulting LPCL/ABS composites clearly showed non-Einstein viscosity phenomena, exhibiting reduced viscosity (2130 Pa·s) compared to …

Implementation Of Multivariate Artificial Neural Networks Coupled With Genetic Algorithms For The Multi-Objective Property Prediction And Optimization Of Emulsion Polymers, David Chisholm

Master's Theses

Machine learning has been gaining popularity over the past few decades as computers have become more advanced. On a fundamental level, machine learning consists of the use of computerized statistical methods to analyze data and discover trends that may not have been obvious or otherwise observable previously. These trends can then be used to make predictions on new data and explore entirely new design spaces. Methods vary from simple linear regression to highly complex neural networks, but the end goal is similar. The application of these methods to material property prediction and new material discovery has been of high interest …

Using Green Emitting Ph-Responsive Nanogels To Report Environmental Changes Within Hydrogels: A Nanoprobe For Versatile Sensing, Mingning Zhu, Dongdong Lu, Shanglin Wu, Qing Lian, Wenkai Wang, L. Andrew Lyon, Weiguang Wang, Paulo Bártolo, Brian R. Saunders

Engineering Faculty Articles and Research

Remotely reporting the local environment within hydrogels using inexpensive laboratory techniques has excellent potential to improve our understanding of the nanometer-scale changes that cause macroscopic swelling or deswelling. Whilst photoluminescence (PL) spectroscopy is a popular method for such studies this approach commonly requires bespoke and time-consuming synthesis to attach fluorophores which may leave toxic residues. A promising and more versatile alternative is to use a pre-formed nanogel probe that contains a donor/acceptor pair and then “dope” that into the gel during gel assembly. Here, we introduce green-emitting methacrylic acid-based nanogel probe particles and use them to report the local environment …

Active Polymeric Materials For 3d Shaping And Sensing, Adebola Oyefusi

Theses and Dissertations

Part I: Reprogrammable Chemical 3D Shaping for Origami, Kirigami, and Reconfigurable Molding

Origami- and kirigami-based design principles have recently received strong interest from the scientific and engineering communities because they offer fresh approaches to engineering of structural hierarchy and adaptive functions in materials, which could lead to many promising applications. Herein, we present a reprogrammable 3D chemical shaping strategy for creating a wide variety of stable complex origami and kirigami structures autonomously. This strategy relies on a reverse patterning method that encodes prescribed 3D geometric information as a spatial pattern of the unlocked phase (dispersed phase) in the locked phase …

“Polysoaps” Via Raft Copolymerization To Form Well-Defined Micelles For Water Remediation And Targeted Drug Delivery Applications, Phillip Pickett

Dissertations

Amphiphilic copolymers have become increasingly important for environmental and biological applications due to their behavioral characteristics in aqueous solution. For example, structurally-tailored statistical amphiphilic copolymers or “polysoaps” can self-assemble into micelles or other architectures in water at various concentrations. Polysoaps may be differentiated from small molecule surfactant micelles in their capability to self-assemble into unimolecular associates (unimolecular micelles) with no dependence on concentration. Such micelles offer enormous potential for dispersion of hydrophobic species in water at high dilution. Importantly, each polymer chain forms its own micelle and upon dilution, these micelles remain intact and capable of dispersing hydrocarbon material in …

Engineering Multifunctional And Morphologically Diverse Polymer Brush Surfaces, Cassandra M. Reese

Dissertations

The combination of surface-initiated polymerization (SIP) and post-polymerization (PPM) serves as a powerful approach to fabricate complex, multifunctional polymer films, which can be precisely tuned for desired surface engineering applications. Careful manipulation of PPM parameters such as reaction conditions, the tethered brush parameters, and the physical properties of the unbound post-modifier greatly influence the depth of penetration of the post-modifier and the polymer brush compositional heterogeneity. This dissertation focuses on engineering polymer brush surfaces with multifunctional chemistries and tunable morphologies by investigating the PPM parameters that dictate the distribution of post-modifiers on grafted polymer brush surfaces.

The first chapter of …

Nanogels And Microgels: From Model Colloids To Applications, Recent Developments, And Future Trends, Mattias Karg, Andrij Pich, Thomas Hellweg, Todd Hoare, L. Andrew Lyon, J. J. Crassous, Daisuke Suzuki, Rustam A. Gumerov, Stefanie Schneider, Igor I. Potemkin, Walter Richtering

Engineering Faculty Articles and Research

Nanogels and microgels are soft, deformable, and penetrable objects with an internal gel-like structure that is swollen by the dispersing solvent. Their softness and the potential to respond to external stimuli like temperature, pressure, pH, ionic strength, and different analytes make them interesting as soft model systems in fundamental research as well as for a broad range of applications, in particular in the field of biological applications. Recent tremendous developments in their synthesis open access to systems with complex architectures and compositions allowing for tailoring microgels with specific properties. At the same time state-of-the-art theoretical and simulation approaches offer deeper …

Deswelling Induced Morphological Changes In Dual Ph And Temperature Responsive Ultra-Low Crosslinked Poly (N-Isopropyl Acrylamide)-Co-Acrylic Acid Microgels, Molla R. Islam, Maddie Tumbarello, L. Andrew Lyon

Engineering Faculty Articles and Research

Poly(N-isopropylacrylamide) microgels prepared without exogenous cross-linker are extremely “soft” as a result of their very low cross-linking density, with network connectivity arising only from the self-crosslinking of pNIPAm chains. As a result of this extreme softness, our group and others have taken interest in using these materials in a variety of bioengineering applications, while also pursuing studies of their fundamental properties. Here, we report deswelling triggered structural changes in poly(N-isopropylacrylamide-co-acrylic acid) (ULC10AAc) microgels prepared by precipitation polymerization. Dynamic light scattering suggests that the deswelling of these particles not only depends on the collapse of …

Conducting Polymer Based Gel Electrolytes For Ph Sensitivity, Aditya Jagannath Kashyap

USF Tampa Graduate Theses and Dissertations

The evaluation of concentration of ions and molecules with the help of biosensors have been regarded as an emerging technology. Bio and chemical sensors have a variety of applications in the field of medicine, military, environmental and food industries alike. With an estimated investment growth of over 4.31% in the development of pH sensors in the next five year, the objective of a developing a robust measurement system is all the more required. The scope of this research is to evaluate the ability of conducting polymer-based gel electrolytes for pH sensitivity, as a function of the transistor characteristics using an …

Development Of In Situ Forming Hydrogels For Intra-Articular Drug Delivery, Andy Prince

Electronic Thesis and Dissertation Repository

Hydrogels are 3-dimensional crosslinked polymer networks that can absorb significant amounts of water. The physical properties associated with hydrogels affords them resemblance to biological tissues making them good candidates for biomedical applications. Many pharmaceuticals, specifically non-steroidal anti-inflammatory drugs (NSAIDs), have poor aqueous solubility, which limits their bioavailability and efficacy. People suffering from chronic osteoarthritis (OA) are required to frequently take large doses to mitigate pain, which can lead to serious side effects. Hydrogels are good strategies to deliver NSAIDs via articular injection because they can form solid gels in situ. This thesis describes the synthesis, formulation, mechanical testing, in …

Uv-Curable Organic-Inorganic Hybrid Polyurethane Coating, Shiyin Yu

Master's Theses and Doctoral Dissertations

This thesis explored a series of organic-inorganic hybrid polyurethane oligomers with varying molecular weights and functional groups (acrylate and/or silane) that were cured with a single ultraviolet (UV) trigger but two photo-initiators. Upon UV irradiation, the free-radical initiator initiated a free-radical reaction for acrylate cross-linking, and the photo-latent base initiated a sol-gel reaction for condensation of the silanes. This study explored the cure extent of both reactions by FTIR for acrylates and silanes and a weight-loss method for silanes as a function of functional group concentration and time. The general film properties were also studied. The results showed that the …

Multidimensional Mass Spectrometry Of Chemonic™ Ccg-6 Nonionic Surfactant With Separation By Polarity And Shape, Charles Johnson

Williams Honors College, Honors Research Projects

Chemonic™ CCG-6 surfactant is a water-soluble poly(ethylene glycol) (PEG) conjugated alkyl glyceride emollient. This surfactant exists as a complex mixture of a glycerol cores conjugated with poly(ethylene glycol) branches (PEGylation) that were partially esterified with caprylic (C8) and capric (C10) acids. These may be esterified on one, two, or all three arms of the glyceride. The architecture of the structures in this mixture was studied using multidimensional mass spectrometry (MS). Mass spectrometry was interfaced with ultra-performance liquid chromatography (UPLC) and ion mobility (IM) separation. The mixture was separated by reversed-phase LC, oligomers of the star-branched polymer were separated according to …

Polyurea Aerogels: From Nanoscopic To Macroscopic Properties, Tahereh Taghvaee

Doctoral Dissertations

"The morphology of a material is intrinsically a qualitative property and in order to relate nanomorphology to synthetic conditions, it is necessary to express nano/micro-structure quantitatively. In this context, polyurea aerogels were chosen as a model system with demonstrated potential for rich nanomorphology and being guided by a statistical Design-of-Experiments model, a large array of materials (208) with identical chemical composition, but quite different nanostructures were prepared. By reflecting upon the SEM images, it was realized that our first pre-verbal impression about a nanostructure is related to its openness and texture; the former is quantified by porosity (Π), and the …

Synthesis And Applications Of Ceramic (Silicon Carbide And Silicon Nitride), Metallic (Cobalt(0)) And Polymeric (Polyurethane) Aerogels, Parwani M. Rewatkar

Doctoral Dissertations

"A new method has been demonstrated for the synthesis of monolithic ceramic and purely metallic aerogels from xerogel powder compacts, and the use of polyurethane aerogels based on cyclodextrins as efficient desiccants.

I. Highly porous ( > 80%) monolithic SiC and Si₃N₄, aerogels were prepared from compressed compacts of polyurea-crosslinked silica xerogel powders. The process is time efficient as solvent-exchange through powders is fast, and energy efficient as it bypasses drying with supercritical fluids. The final ceramic objects were chemically pure, sturdy, with compressive moduli at 37 ±7 MPa and 59 ± 7 MPa, and thermal conductivities …

Novel Adsorbent For Industrial Wastewater Treatment Applications, Islam M. Al-Akraa, Ahmed Y. Zakaria Eng, Dalia A. Ali Eng, Hany A. Elazab Dr, Hoda A. Elsawy Dr

Chemical Engineering

In this study, the hydroxyapatite powder is investigated for both of methylene blue and thymol blue in aqueous solution. The physical and chemical properties of the adsorbent were evaluated systematically using the different techniques including Microsoft Excel programming, linear regression model and also the coefficient of determination. Batch adsorption experiments were conducted to determine the effect of contact time, solution pH, initial dye concentrations, and also the adsorbent dosage on adsorption. The adsorption kinetic parameters confirmed the better fitting of pseudo-second order kinetic model for both of methylene blue and thymol blue. The isotherm data of methylene blue and thymol …

Nanomorphology Dependent Optical And Mechanical Properties Of Aerogels, Chandana Mandal

Doctoral Dissertations

"Aerogels are very low density, light weight open pore materials. A hypothesis that is under intense current investigation by the scientific community states that the mechanical properties of nanostructured polymers depend on their nanomorphology. Aerogels are nanostructured ultra-lightweight nanoporous materials with skeletal frameworks that can display a wide range of nanomorphologies. Thereby aerogels comprise a suitable platform for testing not only that hypothesis but also a wide range of other properties such as light scattering for applications, for example, in thermally insulating windows.

To study the mechanical properties of nanostructured matter as a function of nanomorphology, various shape-memory polyurethane aerogels …