Engineering Commons^™

Characterization Of 3d Printed Polylactic Acid/ Polycaprolactone/Titanium Dioxide Composites For Bone Replacement And Grafting, Sandra Elena Najera Beltran

Open Access Theses & Dissertations

A material that mimics the properties of bones was developed by optimizing the ratio of polymer composites of polylactic acid (PLA) and poly-ε-caprolactone (PCL), containing small amounts of titanium oxide (TiO2). Although titanium-based alloys have commonly been used for bone replacement procedures due to their biocompatibility with the human body and their mechanical properties, stress shielding continues to be a problem. The structure of a bone has a porosity which permits the flow of nutrients, blood, oxygen and minerals, and is an issue at the time of creating bone replacements using conventional methods. PLA and PCL have been used in …

Synthesis And Characterization Of Glycidyl Methacrylate-Based Graft Copolymer Functional Interfaces, Nikolay Brordinov

All Dissertations

Modification of materials properties such as surface energy, wettability, ability to absorb, contain or release specific type of chemicals enables practical application of these materials in various scientific and engineering set-ups. However, designing protocol that could be easily adapted for different situations and simultaneously unlock multiple variations of the resulting properties is a non-trivial task. This dissertation is devoted to application of glycidyl methacrylate-based graft copolymers for the purposes of surface modification, establishing fundamental trends and dependencies of this process and exploring the possible range of applications. These materials have extremely valuable property to undergo controllable post-synthetic modifications including surface …

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 …

Strategies For Controlling Bulk Heterojunction Morphology, Zach Daniel Seibers

Doctoral Dissertations

Organic photovoltaic devices have been extensively studied as a means to produce sustainable energy. However, the performance of organic-photovoltaic (OPV) devices is dependent upon a number of factors including the morphology of the active layer, device architecture, and processing conditions. Recent research has indicated that fullerenes in the bulk heterojunction are entropically driven to the silicon and air interfaces upon crystallization of P3HT, which occurs during thermal annealing. The first chapter of this research focuses on investigating the structure and function of end-tethered poly(3-hexylthiophene) chains to a transparent electrode as an anode buffer layer. Neutron reactivity reveals that these P3HT …

Size Scaling Of Strength And Toughness For 3d Printed Polymer Specimens, Darren Thomas Bell

Open Access Theses

To find material systems that offer low density and high strength, stiffness or toughness, hierarchically designed material systems have provided a promising research area. This thesis lays the groundwork for designing efficient micro-architectured material systems by characterizing size effects for 3d printed polymer parts. Two methods were used to analyze data from 3-point bend tests for specimens of varying size: the load-separation method was used for finding the point of crack growth initiation and Bazant’s method was used to find shape independent strength at failure. The strength values were used as inputs for finding size independent material constants within a …

Cold Gas Dynamic Spray – Characterization Of Polymeric Deposition, Trenton Bush

Masters Theses

When a solid, ductile particle impacts a substrate at sufficient velocity, the resulting heat, pressure, and plastic deformation can produce bonding at the interface. The use of a supersonic gas flow to accelerate such particles is known as Cold Spray deposition. The Cold Spray process has been commercialized for some metallic materials, but further research is required to unlock the exciting material properties possible with polymeric compounds. In this work, a combined computational and experimental study a) simulated and optimized the nozzle flow conditions necessary to produce bonding in a polyethylene particle, b) developed and fabricated an experimental device, and …

Improving The Mechanical Performance Of 3d Printed Parts Using Fused Filament Fabrication, Inderpreet Binning

Industrial and Manufacturing Engineering

The 3D printing industry has seen rapid growth in the last 10 years and has been called the next industrial revolution. There are several different processes used in 3D printing, but the most popular process is called Fused Filament Fabrication (FFF) or Fused Deposition Modeling (FDM). This is the process where (most commonly) plastic filament enters a nozzle, is heated to a semi-liquid state, and then deposited into a pattern to create a print. One major drawback to this process is that the prints are anisotropic. This means that the strength of the print varies with the orientation that it …

Magnetic, Optical And Electrical Properties Of Electron-Hole Pairs In Polymer And Organo-Metal Halide Perovskite Photovoltaic Cells, Yu-Che Hsiao

Doctoral Dissertations

Organic polymer and organo-metal halide perovskite (OMHP) materials have attracted extensive attention during the past decade due to their various applications, like solar cells, light emitting diode, even lasing action (OMHP). Especially, the organo-metal halide perovskite solar cell shows a remarkable power conversion efficiency of about 20%, which is comparable to the amorphous silicon solar cell. Therefore, OMHP solar cell had been considered as a promising substitution for the next generation of renewable energy source. The OMHP materials contain both advantages of organic and inorganic semiconductors, like solution processable thin film fabrication, long-range ambipolar transport characteristics, high dielectric constants, low …

Synthesis Of Acceptors For Use In Donor-Acceptor Copolymers And Characterization Of These Polymers, William D. Walker

Honors Theses

In this thesis, a selenium-derivatized acceptor was synthesized to examine the heavy atom effects of selenium on the position of the frontier molecular orbitals (HOMO/LUMO band gap) as opposed to sulfur in a donor-acceptor copolymer for use in light harvesting and detection applications. Over the course of this research, standard operating protocols for ultraviolet-visible (UV-Vis-NIR) and Fourier transform infrared (FT-IR) spectroscopies, as well as cyclic voltammetry (CV) characterization techniques were established. Once synthesized, the polymers were characterized through use of the established characterization protocols. The selenium-derivatized polymer exhibited a bathochromic shift compared to the sulfur analogue, with a solid-state absorption …

Synthesis And Characterizations Of Stimuli-Responsive Polymeric Materials For Biomedical Applications, Shuangcheng Tang

Doctoral Dissertations

Stimuli-responsive polymeric materials have been now widely researched toward the biomedical applications including therapeutic delivery, bio-sensor surface modification, and tissue-engineering, etc., considering their desirable biocompatibility, tunable properties, and sensitivity toward physiological stimuli. Beyond the monoresponsive materials, polymers with responsiveness simultaneously toward multiple stimuli are paid great attention to because the control of responsive behaviors could be achieved at a more accurately and delicately level in a complex local environment. However, many challenges still exist such as maintaining integrity of the structure, shaping the morphology at micro- and macro-scale, and regulating a controllable and predictable transition behavior.

The objectives of this …

Effect Of Processing History And Material Properties On The Growth Of Wrinkle Amplitude, Yu-Cheng Chen

Doctoral Dissertations

Wrinkling has been employed by many organisms to form unique topography, such as fingerprints, gut villi, and surface of flower petal cells. The wavy wrinkle structure provides friction enhancement, surface area increase, optical, and wetting properties improvement. Inspired by Nature, scientists have created wrinkles synthetically and proposed numerous uses for them. However, wrinkling surfaces encounters limitations on achieving massive area and high amplitude-to-wavelength ratio (aspect ratio). The three phase contact line wrinkling technique creates well-defined wrinkles in a continuous fashion, and has great potential to scale-up for massive production. In addition to the velocity dependent adhesion force, we find the …

Measuring Polydimethylsiloxane (Pdms) Mechanical Properties Using Flat Punch Nanoindentation Focusing On Obtaining Full Contact, Federico De Paoli

USF Tampa Graduate Theses and Dissertations

In this research, the materials used were the Polydimethylsiloxane (PDMS) polymers. PDMS mechanicals properties were measured using a customized version of the nanoindentation test using a flat punch tip. The method is proposed in Chapter 3 and it is used to calculate the elastic modulus of different PDMS samples. The samples tested were both produced specifically for this research and available in the laboratory’s storage. They all present different levels of cross-linking degree.

It is quite common to not have full contact between the cylindrical flat punch and the sample because of the unavoidable tilt. The new method guarantees establishing …

Tunable Photonic Multilayers From Stimulus-Responsive, Photo-Crosslinkable Polymers, Maria C. Chiappelli

Doctoral Dissertations

This dissertation describes the synthesis of photo-crosslinkable copolymers and their utilization for the fabrication and testing of tunable and responsive one-dimensional (1D) photonic multilayers. Photonic multilayers exhibit structural color due to the interference of incident light at layer interfaces, providing a convenient route towards optically responsive materials that do not rely on potentially light- or oxygen-sensitive chromophore-containing pigments and dyes. A fabrication technique based on sequential spin-coating and crosslinking of photo-crosslinkable polymers is used to assemble tunable and responsive photonic multilayers. Chapter One introduces the fundamental underlying principles of 1D photonic structures and explores their importance in a variety of …

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 …

Wear Resistant Polydopamine/Ptfe Nanoparticle Composite Coating For Dry Lubrication Applications, Samuel George Beckford

Graduate Theses and Dissertations

This dissertation presents an investigation into the effect of nanoparticle fillers and a polydopamine adhesive primer on the tribological performance of thin PTFE films. The principal objective of this investigation was to reduce wear in PTFE films, an issue which precludes the use of PTFE films in tribological applications requiring high durability. The friction and wear of the composite films were evaluated using a ball-on-flat configuration in linear reciprocating motion. It was found that the use of a polydopamine adhesive primer reduces the wear of PTFE films more than 600 times. X-ray photoelectron spectroscopy (XPS) results show that a tenacious …

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 …

Surfactant Assisted Dispersion Of Single-Walled Carbon Nanotubes In Polyvinylpyrrolidone Solutions, Tennison Yu

Electronic Thesis and Dissertation Repository

Obtaining stable aqueous dispersions is one of the main challenges hindering a widespread and effective use of single-walled carbon nanotubes (SWNT) in many applications. Although it has been recognized that their versatility makes them an extremely attractive material, the unique molecular structure that gives SWNTs their unmatched electronic, mechanical, and thermal properties is also responsible for strong van der Waals interactions. This, combined with extremely high aspect ratios and flexibility, causes SWNTs to adhere strongly into tightly bundled ropes. In these bundles, SWNTs are not as useful as their linearized unbundled equivalents. Thus, in order to take advantage of their …

Mechanical Behavior Of Compression Molded Polyethylene Terephthalate, Daniel Cole Greinke, Paul Jackson Mcewan, Dan Tran

Materials Engineering

The purpose of this project was to investigate the effects of time, temperature, and pressure on the tensile strength and elastic modulus of recycled PET. Compression molding trials were performed on shredded PET bottles to produce tensile test specimens conforming to ASTM D638-03. Aluminum molds containing the PET were mechanically fastened together at the desired pressure and heated in an electric oven. The resulting specimens were subjected to tensile testing for analysis. This screening experiment failed to generate any statistically significant data concerning the factors of interest. These preliminary results may be used to design a more systematic follow-up study.

An Investigation Into The Properties And Fabrication Methods Of Thermoplastic Composites, Ann E. Livingston-Peters

Master's Theses

As applications for thermoplastic composites increase, the understanding of their properties become more important. Fabrication methods for thermoplastic composites continually improve to match designs specifications. These advanced thermoplastics have begun to show an improvement in mechanical properties over those found in thermoset composites commonly used in industry. Polyaryletherketones (PEK) have high service temperatures, good mechanical properties, and improved processing capabilities compared to thermoplastics used in the past making them important to the aerospace industry. The wide range of types of PEK make them suitable for a variety of applications, but selection of specific chemistries, processing parameters, and composite stack-ups determine …

Stress Corrosion Cracking In Polymer Matrix Glass Fiber Composites, Jonathan Kosak

Electronic Theses and Dissertations

With the use of Polymer Matrix Glass Fiber Composites ever expanding, understanding conditions that lead to failure before expected service life is of increasing importance. Stress Corrosion Cracking (SCC) has proven to be one such example of conditions found in use in high voltage transmission line applications that leads to brittle fracture of polymer matrix composites.

SCC has been proven to be the result of acid buildup on the lines due to corona discharges and water buildup. This acid leaches minerals from the fibers, leading to fracture at low loads and service life. In order to combat this problem, efforts …

Electroplating Of Nanoengineered Polymer Substrate, Brandon Voelker

Masters Theses

The development of a polyethylene based polymer with metallic inclusions, a nanoengineered polymer, has recently opened up great potential for many new commercial and industrial applications. The major advantage of developing these nanoengineered polymers is to be able to tailor the resistance and other properties by varying the composition of the polymer. The industrial usage of this polymer benefits from the addition of an electrically conductive, metallic coating. This research develops methods of electroplating nickel and copper layers on to the polymer substrates using DC and pulsed techniques.

Electroplating is conducted in a 1000 mL beaker using a specialized plating …

Investigation Of Energy Alignment Models At Polymer Interfaces, Wenfeng Wang

USF Tampa Graduate Theses and Dissertations

The presented study investigated the Induced Density of Interface States (IDIS) model at different polymer interfaces by using photoemission spectroscopy in combination with electrospray deposition.

In recent years, organic electronics have attracted considerable attention due to their advantages of low-cost and easy-fabrication. The performance of such devices crucially depends on the energy barrier that controls the interface charge transfer. A significant effort has been made to explore the mechanisms that determine the direction and magnitude of charge transfer barriers in these devices. As a result of this effort, the IDIS model was developed to predict the energy alignment at metal/organic …

The Effect Of Processing Parameters On Barrier Properties Of Polymers, Russell Louis Hallman Jr.

Doctoral Dissertations

The intent of this work was to learn if polyethylene could be made with predictable water transfer rates by control of the microstructure. A series of films were formed from three different polyethylenes with a range crystallinities using melt pressing, a controlled cooling rate, and subsequent heat treatments. The samples were tested on a novel device called the polymer characterization device that measures the water transfer flux as a function of temperature. The samples’ morphology was examined using differential gradient column, differential scanning calorimetry, Fourier transform infrared microscopy, wide-angle X-ray diffractions, small-angle X-ray scattering, and small angle light scattering, and …

Tuning Cell Fate On Self-Assembled Structures, Xiaohui Wu

Doctoral Dissertations

This dissertation presents novel biodegradable copolymers with dendritic architecture, classic polymers, and inorganic materials with controlled surface topography, stiffness, and surface energy for investigating cell-material interactions and targeting tissue engineering applications. Chapter I reviews the recent progress in bone and nerve regeneration, the key factors of materials influencing cell-material interaction, and self-assembled polymer structures. Chapter II presents a divergent method to synthesize biodegrable com-dendritic tri-block copolymers consisting of poly(ethylene glycol) and poly(L-lactide) or poly(ε-caprolactone) and the MC3T3-E1 cell response to their spherulites. Chapter III presents the fabrication of deformable poly(ε-caprolactone) honeycomb films prepared via a surfactant-free breath figure method in …

Preparation Of A Polylactic Acid With Hydroxyapatite Reinforcement Composite, Odessa N. Quezon

Materials Engineering

Biodegradable polymers are a prime material choice for temporary biomedical devices due to its ability to degrade into non-toxic products for their use in vivo. However, polylactic acid (PLA) by itself lacks the sufficient strength and stiffness to permit their use as its properties begin to decrease as the polymer degrades. To improve the polymer’s mechanical properties, hydroxyapatite (HA) will be added to the PLA solution to act as reinforcement. The chemical property, glass transition temperature of a polymer, also plays a key role in the mechanical properties of the polymer. PLA’s glass temperature is 130⁰F. A polymer that …

Engineering Single-Molecule, Nanoscale, And Microscale Bio-Functional Materials Via Click Chemistry, Michael Daniele

All Dissertations

To expand the design envelope and supplement the materials library available to biomaterials scientists, the copper(I)-catalyzed azide-alkyne cycloaddition (CuCAAC) was explored as a route to design, synthesize and characterize bio-functional small-molecules, nanoparticles, and microfibers. In each engineered system, the use of click chemistry provided facile, bio-orthogonal control for materials synthesis; moreover, the results provided a methodology and more complete, fundamental understanding of the use of click chemistry as a tool for the synergy of biotechnology, polymer and materials science. Fluorophores with well-defined photophysical characteristics (ranging from UV to NIR fluorescence) were used as building blocks for small-molecule, fluorescent biosensors. Fluorophores …

Probing And Controlling Fluid Rheology At Microscale With Magnetic Nanorods, Alexander Tokarev

All Dissertations

This Dissertation is focused on the development of new methods for characterization and control of fluid rheology using magnetic nanorods. This Dissertation consists of five chapters. In the first chapter, we review current microrheologial methods and develop a Magnetic Rotational Spectroscopy (MRS) model describing nanorod response to a rotating magnetic field. Using numerical modeling, we analyze the effects of materials parameters of nanorods and fluids on the MRS characteristic features. The model is designed for a specific experimental protocol. We introduce and examine physical parameters which can be measured experimentally. The model allows identification of MRS features enabling the calculation …

The Mitigation Of Eutrophication Using Microporous Polymer Membranes To Control Algae Growth, Christopher R. Riley

Materials Engineering

A system was designed to mitigate the accelerated process of anthropogenic eutrophication. This system aimed to contain Chlorella Vulgaris microalgae cells within an enclosed polymer membrane pouch while allowing for water and nutrients to diffuse through the pouch. As a test model, a 10 gallon aquarium was partitioned into three sections using polycarbonate membranes with 1 micron pore diameters. Each section was then gradually filled with a deionized water and Bristol solution recommended for microalgae growth. Phosphate and nitrate were added to Section A of the aquarium and allowed to diffuse throughout the tank. A water pump was used to …

Multipolymer Interactions In Bulk Heterojunction Photovoltaic Devices, Grant Olson

Physics

Multipolymer photovoltaics, single layer devices made up of multiple photoactive polymers, can create organic photovoltaics (OPVs) with a wider spectral response than single polymer systems without the difficult fabrication of a tandem. Our group has successfully created multipolymer solar devices with 2% power conversion efficiency. We have analyzed the optical and electrical properties of these devices, and found that it may be possible for polymers to assist each other with charge extraction, though combining polymers disrupts single polymer crystallinity.

Tuning The Properties Of Metal-Ligand Complexes To Modify The Properties Of Supramolecular Materials, Ian Henderson

Open Access Dissertations

Supramolecular chemistry is the study of discreet molecules assembled into more complex structures though non-covalent interactions such as host-guest effects, pi-pi stacking, electrostatic effects, hydrogen bonding, and metal-ligand interactions. Using these interactions, complex hierarchical assembles can be created from relatively simple precursors.

Of the supramolecular interactions listed above, metal-ligand interactions are of particular interest due to the wide possible properties which they present. Factors such as the denticity, polarizability, steric hindrance, ligand structure, and the metal used (among others) contribute to a dramatic range in the physical properties of the metal-ligand complexes. Particularly affected by these factors are the kinetic …