Engineering Commons^™

Two-Component Hydrogel As Biomimetic Vitreous Substitutes, Sruthi Santhanam

McKelvey School of Engineering Theses & Dissertations

The vitreous humor of the eye is a biological hydrogel principally composed of fibrillary collagen interspersed with semi-flexible polyelectrolyte, hyaluronic acid (HA). Certain pathological conditions necessitate its removal and replacement. Current vitreous substitutes, such as silicone oils and perfluorocarbons, are hydrophobic, do not resemble the properties of the vitreous, and have known complications. An ideal vitreous substitute should have properties of the natural vitreous, perform its functions, and be biocompatible in the eye. Inspired by the structure and composition of the natural vitreous, we used bio-mimicry to develop an injectable two-component hydrogel. The hydrogel is composed of a fibrillary gellan, …

Cellulose Nanofiber-Reinforced Impact Modified Polypropylene: Assessing Material Properties From Fused Layer Modeling And Injection Molding Processing, Jordan Elliott Sanders

Electronic Theses and Dissertations

The purpose of this research was to investigate the use of cellulose nanofibers (CNF) compounded into an impact modified polypropylene (IMPP) matrix. A IMPP was used because it shrinks less than a PP homopolymer during FLM processing. An assessment of material properties from fused layer modeling (FLM), an additive manufacturing (AM) method, and injection molding (IM) was conducted. Results showed that material property measurements in neat PP were statistically similar between IM and FLM for density, strain at yield and flexural stiffness. Additionally, PP plus the coupling agent maleic anhydride (MA) showed statistically similar results in comparison of IM and …

Development Of High-Performing Polydimethylsiloxane-Based Membranes For Carbon Dioxide Separation, Tao Hong

Doctoral Dissertations

Membrane separation is highlighted as one of the most promising approaches to mitigate the excessive CO₂ [carbon dioxide] emission, due to its significant reduction of energy cost compared with many conventional separation techniques. Unfortunately, the separation performance of current membranes does not meet the practical CO₂/N₂ [nitrogen] separation requirements. And due to the huge volume of industrial flue gas, membranes with exceptionally high permeability are needed for practical reasons.

Currently, the separation mechanism of most polymeric membranes is based on size-sieving. However, this method is not sufficient for CO₂/N₂ separations due to the …

Responsive Nanogel Probe For Ratiometric Fluorescent Sensing Of Ph And Strain In Hydrogels, Mingning Zhu, Dongdong Lu, Shanglin Wu, Qing Lian, Wenkai Wang, Amir H. Milani, Zhengxing Cui, Nam T. Nguyen, Mu Chen, L. Andrew Lyon, Daman J. Adlam, Anthony J. Freemont, Judith A. Hoyland, Brian R. Saunders

Engineering Faculty Articles and Research

In this study a new pH-responsive nanogel probe containing a complementary nonradiative resonance energy transfer (NRET) fluorophore pair is investigated and its ability to act as a versatile probe of network-related changes in three hydrogels demonstrated. Fluorescent sensing using NRET is a powerful method for studying relationships between Angstrom length-scale structure and macroscopic properties of soft matter. Unfortunately, inclusion of NRET fluorophores into such materials requires material-specific chemistry. Here, low concentrations of preformed nanogel probes were included into hydrogel hosts. Ratiometric photoluminescence (PL) data for the gels labeled with the nanogel probes enabled pH-triggered swelling and deswelling to be studied …

Hybrid Polymer Electrolyte For Lithium-Oxygen Battery Application, Amir Chamaani

FIU Electronic Theses and Dissertations

The transition from fossil fuels to renewable resources has created more demand for energy storage devices. Lithium-oxygen (Li-O₂) batteries have attracted much attention due to their high theoretical energy densities. They, however, are still in their infancy and several fundamental challenges remain to be addressed. Advanced analytical techniques have revealed that all components of a Li-O₂ battery undergo undesirable degradation during discharge/charge cycling, contributing to reduced cyclability. Despite many attempts to minimize the anode and cathode degradation, the electrolyte remains as the leading cause for rapid capacity fading and poor cyclability in Li-O₂ batteries. In this …

Cellulose Reinforced Thermoplastic Composites By In-Situ Ring-Opening Polymerization, Shahab Kashani Rahimi

Dissertations

Over the past two decades, the increasing concern about the negative environmental impacts of synthetic materials has led to rising interests in utilizing renewable natural resources to develop polymer materials with comparable properties and performance to their synthetic counterparts. One of the major fields of interest is polymer composites where the replacement of synthetic fibers with bio renewable natural fibers is of great potential. However, the processing difficulties, in terms of fiber dispersion and thermal stability have limited the application of cellulosic fibers to polymers with low processing temperatures which are mostly hydrophobic polymers. As a result, the true reinforcing …

Photopolymerization Synthesis Of Magnetic Nanoparticle Embedded Nanogels For Targeted Biotherapeutic Delivery, Daniel Jonwal Denmark

USF Tampa Graduate Theses and Dissertations

Conventional therapeutic techniques treat the patient by delivering a biotherapeutic to the entire body rather than the target tissue. In the case of chemotherapy, the biotherapeutic is a drug that kills healthy and diseased cells indiscriminately which can lead to undesirable side effects. With targeted delivery, biotherapeutics can be delivered directly to the diseased tissue significantly reducing exposure to otherwise healthy tissue. Typical composite delivery devices are minimally composed of a stimuli responsive polymer, such as poly(N-isopropylacrylamide), allowing for triggered release when heated beyond approximately 32 °C, and magnetic nanoparticles which enable targeting as well as provide a mechanism for …

A Comparison Study Of Two Synthesis Methods For Polymer Of Intrinsic Microporosity 1 (Pim-1), Conor S. Perry

Materials Engineering

Polymers of Intrinsic Microporosity (PIMs) are an emerging polymeric material class for molecular sieving applications. This study focuses on PIM-1, an alternating copolymer of 5,5’,6,6’-tetrahydroxy-3,3’,3,3’-tetramethyl-1,1’-spirobisindane and tetrafluoroterephthalonitrile synthesized via nucleophilic aromatic substitution. PIM-1 been widely studied as a gas separating material and filtering membrane, but in this case, it is studied as a battery separator material. PIM-1’s microporous (pore diameters less than 2 nm) structure allows smaller favorable ions to transport while preventing larger ions and compounds from transporting. Two synthesis methods, round bottom flask synthesis and ball mill synthesis, of PIM-1 are compared to see any improved characteristics. The …

Synthesis And Characterization Of Molybdenum Sulfide And For Hydrogen Evolution Reaction And Supercapacitor Applications, Zhuo Wang

Electronic Theses & Dissertations

To meet the constantly rising requirement of energy other than traditional fossil fuel and environment protection, it is a perfect time to development low cost, and efficient materials for clean energy production. Hydrogen generation by water splitting is one of the cleanest ways to produce cheaper energy. Hydrogen evolution reaction (HER) is one of the key steps in water splitting process. Ideally, the thermodynamic potential for HER should be at 0 V (vs. SHE). However, without an efficient catalyst, this reaction occurred at higher potential, called overpotential. A good HER catalyst is needed to lower the overpotential and hence to …

Effect Of Crosslinking On Carbon Nanotube Materials Through Chemical Treatment And Irradiation, Xinyi Lu

Doctoral Dissertations

Carbon nanotubes (CNTs) exhibit a variety of exceptional properties, especially their ultrahigh tensile strength on the order of 100GPa show promise for constituting the next-generation carbon fiber. However, challenges remain to translate these properties into useful technology, primarily due to the sliding of the tubes past one another under tensile loading. The work presented in this dissertation is focused on enhancing the interaction between the CNTs and their bundles in a macro-assembly, in order to improve the tensile properties of the material.

Applying inter-tube crosslinks has been predicted to significantly enhance the stress transfer between the CNT components. We developed …

Formation Of Nanostructured Epoxy Networks Containing Polyhedral Oligomeric Silsesquioxane (Poss) And Silica Nanoparticles, Amit K. Sharma

Dissertations

This dissertation is focused on structure-property-processing relationship studies based on well-defined polyhedral oligomeric silsesquioxane (POSS) modified epoxy networks to present a comprehensive understanding of hybrid network behavior. In this research, a monoamine functional POSS molecule is incorporated into the epoxy monomer as pendant unit to mimic common epoxy structures and then crosslinked to form well-defined epoxy hybrid networks. The POSS cages behave as nanosized pendant unit in the epoxy matrices, while the mass fraction of POSS cages is varied and the effects on physical properties are examined with respect to changes in network architecture.

A novel continuous reactor method is …

Effect Of Chain Rigidity On Network Architecture And Deformation Behavior Of Glassy Polymer Networks, Kyler Reser Knowles

Dissertations

Processing carbon fiber composite laminates creates molecular-level strains in the thermoset matrix upon curing and cooling which can lead to failures such as geometry deformations, micro-cracking, and other issues. It is known strain creation is attributed to the significant volume and physical state changes undergone by the polymer matrix throughout the curing process, though storage and relaxation of cure-induced strains remain poorly understood. This dissertation establishes two approaches to address the issue. The first establishes testing methods to simultaneously measure key volumetric properties of a carbon fiber composite laminate and its polymer matrix. The second approach considers the rigidity of …

All Acrylic Based Thermoplastic Elastomers: Design And Synthesis For Improved Mechanical Performance, Wei Lu

Doctoral Dissertations

Thermoplastic elastomers (TPEs) have been widely studied because of their recyclability, good processability, low production cost and distinct performance. Compared to the widely-used styrenic TPEs, acrylate based TPEs have potential advantages including exceptional chemical, heat, oxygen and UV resistance, optical transparence, and oil resistance. However, their high entanglement molecular weight lead to “disappointing” mechanical performance as compared to styrenic TPEs. The work described in this dissertation is aimed at employing various approaches to develop the all acrylic based thermoplastic elastomers with improved mechanical performance.

The first part of this work focuses on the introduction of acrylic polymers with high glass …

An Investigation Of The Use Of Cerium And Polyhedral Oligomeric Silsesquioxanes For The Protection Of Polymeric Epoxy Compounds In The Low Earth Orbit Environment, Jessica Miriam Piness

Dissertations

Low Earth orbit presents many hazards for composites including atomic oxygen, UV radiation, thermal cycling, micrometeoroids, and high energy protons. Atomic oxygen and vacuum ultraviolet radiation are of concern for space-bound polymeric materials as they degrade the polymers used as matrices for carbon fiber composites, which are used in satellites and space vehicles due to their high strength to weight ratios. Epoxy-amine thermosets comprise a common class of matrix due to processability and good thermal attributes. Polyhedral oligomeric silsesquioxanes (POSS) have shown the ability to reduce erosion in polyimides, polyurethanes, and other polymers when exposed to atomic oxygen. The POSS …

Design And Synthesis Of Polymer Brush Surfaces With Complex Molecular Architectures And Morphologies, Wei Guo

Dissertations

The combination of surface-initiated polymerization (SIP) and postpolymerization modification (PPM) is a powerful technique for the fabrication of functional soft surfaces. Better understanding the influence of the aforementioned factors on the PPM effectiveness is valuable for fulfilling the potential of the PPM approach for the fabrication of functional soft surfaces. Specifically, by carefully balancing modification reactivity and limitation of mass transport, polymer brush with composition heterogeneity and gradient along the normal direction of the surface otherwise unattainable by methods of direct polymerization can be fabricated via the PPM approach which opens doors to new routes to polymer brush with complex …

Polyisobutylene Telechelic Prepolymers By In Situ End-Quenching And Post-Polymerization Modifications, Bin Yang

Dissertations

This volume focuses on the development of telechelic polyisobutylene (PIB) prepolymers by combining end-capping of living carbocationic polymerization of isobutylene (IB) with suitable reactants and post-polymerization modifications. Alkylation kinetics of PIB tert-chloride with alkoxybenzenes using either TiCl₄ or AlCl₃ were investigated. Quantitative para-position end-capped products were only achieved if the alkoxybenzene/AlCl₃ molar ratio was greater than unity; while no such molar ratio is required for TiCl₄, but the alkylation rate was slower than AlCl₃ under the same conditions. Photopolymerization kinetics analysis of PIB triphenol tri(meth)acrylates with low and high M_ns, …

Exploring Thermoresponsive Affinity Agents To Enhance Microdialysis Sampling Efficiency Of Proteins, Thaddeus Vasicek

Graduate Theses and Dissertations

Affinity agents increase microdialysis protein relative recovery, yet they have not seen widespread use within the microdialysis community due to their additional instrumentation requirements and prohibitive cost. This dissertation describes new affinity agents for microdialysis that require no additional instrumentation to use, have nearly 100% particle recovery, are 7 times more cost efficient than alternatives, and have low specificity enabling their use for a wide variety of proteins. Initially gold nanoparticles were chosen as an affinity ligand support due to their high surface area/volume ratio and colloidal stability. Poly (N-isopropylacrylamide) was immobilized to the gold nanoparticles, which served to sterically …

A Quartz Crystal Microbalance Study Of Thiol:Ene Poly(Ionic Liquid) Polymerization And Gas Absorption, Yueming Wu

Murray State Theses and Dissertations

ABSTRACT

The polymerization process of, and gas absorption by, imidazolium-containing thiol:ene poly (ionic liquid)s (PILs), prepared from bisallylimidazolium bis(trifluoromethyl sulfonyl)imide [NTf₂^-] and pentaerythritoltetrakis(3 mercaptopropionate), was studied. The thiol:ene PILs examined were recently reported by groups at Murray State University. The advantage of thiol:ene PILs over other reported PILs is that thiol:ene polymers are made rapidly by UV exposure and exhibit high mechanical and thermal stability due to high cross-linking. The properties of interest for the thiol:ene PILs were studied using a quartz crystal microbalance (QCM). QCM techniques are based on the piezoelectric effect, where certain crystals (e.g., …