Engineering Commons^™

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 …

Interface And Morphology Engineering In Solution-Processed Electronic And Optoelectronic Devices, Sanjib Das

Doctoral Dissertations

The first part of this dissertation focuses on interface and morphology engineering in polymer- and small molecule-based organic solar cells. High-performance devices were fabricated, and the device performance was correlated with nanoscale structures using various electrical, spectroscopic and microscopic characterization techniques, providing guidelines for high-efficiency cell design.

The second part focuses on perovskite solar cells (PSCs), an emerging photovoltaic technology with skyrocketing rise in power conversion efficiency (PCE) and currently showing comparable PCEs with those of existing thin film photovoltaic technologies such as CIGS and CdTe. Fabrication of large-area PSCs without compromising reproducibility and device PCE requires formation of dense, …

Solution And Surface Properties Of Architecturally- And Compositionally-Complex Block Copolymers And Their Binary Mixtures, Jesse Lawrence Davis

Doctoral Dissertations

The spontaneous generation of complex structures from polymeric building blocks provides a simple yet effective route to create useful soft matter structures having potential application in a variety of nanotechnologies. The topology, chemical structure, block composition, and sequence of the constituent building blocks of polymers are tunable through synthetic chemistry. This tunability offers attractive opportunities to generate complex, yet well-defined structures with control over the geometry, packing symmetry, and microdomain structure. This thesis work involves the study of the self-assembly behaviors of architecturally complex amphiphilic block copolymers (ABCs). ABCs are composed of two or more chemically distinct blocks that are …

Novel Thermoplastic Elastomers Based On Benzofulvene: Synthesis And Mechanical Properties, Weiyu Wang

Doctoral Dissertations

Thermoplastic elastomers (TPEs) are of great importance both academically and technologically. Currently TPEs are the predominated form of styrene-diene copolymers. However, these styrenic TPEs have serious limitations in applications, especially at higher temperature, because of their low upper service temperature (UST). The work described in this dissertation aimed to developing thermoplastic elastomers with a higher UST and lower cost.

In order to develop TPEs with a higher UST, we employed benzofulvene, an anionically polymerizable monomer in hydrocarbon solvent at room temperature, as the glassy block and copolymerized it with isoprene to prepare polybenzofulvene-polyisoprene-polybenzofulvene (FIF) triblock copolymers. Among all triblock copolymers …

Failure Simulations At Multiple Length Scales In High Temperature Structural Alloys, Chao Pu

Doctoral Dissertations

A number of computational methodologies have been developed to investigate the deformation and damage mechanism of various structural materials at different length scale and under extreme loading conditions, and also to provide insights in the development of high-performance materials.

In microscopic material behavior and failure modes, polycrystalline metals of interest include heterogeneous deformation field due to crystalline anisotropy, inter/intra grain or phase and grain boundary interactions. Crystal plasticity model is utilized to simulate microstructure based polycrystalline materials, and micro-deformation information, such as lattice strain evolution, can be captured based on crystal plasticity finite element modeling (CPFEM) in ABAQUS. The comparison …

Ion Irradiation-Induced Microstructural Change In Sic, Chien-Hung Chen

Doctoral Dissertations

The high temperature radiation resistance of nuclear materials has become a key issue in developing future nuclear reactors. Because of its mechanical stability under high-energy neutron irradiation and high temperature, silicon carbide (SiC) has great potential as a structural material in advanced nuclear energy systems.

A newly developed nano-engineered (NE) 3C SiC with a nano-layered stacking fault (SFs) structure has been recently considered as a prospective choice due to enhanced point defect annihilation between layer-type structures, leading to outstanding radiation durability.

The objective of this project was to advance the understanding of gas bubble formation mechanisms under irradiation conditions in …

Kinetic And Thermodynamic Modeling Of Long Term Phase Stability In Alloy 800h Subjected To Lwr Core Conditions, Wayne Ethan Pratt

Masters Theses

An in depth literature review of Incoloy Alloy 800H was conducted and presented to summarize the current understanding of microstructural evolution under irradiation and secondary phase precipitate stability. Due to a lack of radiation induced segregation (RIS) data for Alloy 800H, Isopleth sections varying Cr, Ni, Ti, and Si were generated from a computational thermodynamics approach using ThermoCalc and analyzed to compensate for knowledge related to radiation induced precipitates (RIP’s). These isopleths were analyzed for a composition range based off previous knowledge of RIS tendencies in austenitic stainless steels. Analysis of four major binary phase diagrams and complex phase diagrams …

Incorporation Of High-K Hfo2 Thin Films In A-Igzo Thin Film Transistor Devices, Aaron Hamilton Bales

Masters Theses

In this study, HfO2 [hafnium oxide] thin films are investigated extensively as part of indium gallium zinc oxide (IGZO) thin film transistor (TFT) devices. They are incorporated into the TFTs, both as a gate insulator and a passivation layer. First, the HfO2 [hafnium oxide] films themselves are investigated through an annealing study and through I-V and C-V measurements. Then, HfO2 [hafnium oxide] is suggested as a replacement for commonly used SiO2 [silicon dioxide] gate insulator, as it has a dielectric constant that is 4 – 6 times higher. This higher dielectric constant allows for comparable TFT performance at a lower …

Ion Irradiation Characterization Studies Of Max Phase Ceramics, Daniel William Clark

Masters Theses

The family of layered carbides and nitrides known as MAX phase ceramics combine many attractive properties of both ceramics and metals due to their nanolaminate crystal structure and are promising potential candidates for application in future nuclear reactors. This thesis reports on the background, design, and analysis of an experiment focused on determining the effects of energetic heavy ion irradiations on polycrystalline samples of titanium silicon carbide 312, titanium aluminum carbide 312, and titanium aluminum carbide 211. The irradiation conditions consisted of ion doses between 10 and 30 displacements per atom at temperatures of 400 and 700 degrees Celsius, conditions …

Ion Irradiation Induced Damage And Dynamic Recovery In Single Crystal Silicon Carbide And Strontium Titanate, Haizhou Xue

Doctoral Dissertations

The objective of this thesis work is to gain better understanding of ion-solid interaction in the energy regime where electronic and nuclear energy loss are comparable. Such responses of materials to ion irradiations are of fundamental importance for micro-electronics and nuclear applications. The ion irradiation induced modification for the crystal structure, the physical and chemical properties etc. may strongly affect the performance of functional materials that needs to be better understood.

Experimentally, ion irradiation induced damage accumulation and dynamic recovery in SiC [silicon carbide] and SrTiO₃ [strontium titanate] were studied in this dissertation project. Five chapters are presented: Firstly, …

Crystal Growth And Physical Property Characterization Of Complex Perovskite Oxides, Ling Li

Doctoral Dissertations

Bulk EuTiO₃ [europium titanate], a quantum paraelectric antiferromagnet, is shown to exhibit multiferroic behavior in strained thin film form, which highlights the spin-phonon coupling in this system. We have investigated the structural, elastic, magnetic, thermal and transport properties of single crystals of EuTiO₃ as well as doped system EuTi_1-xB_xO₃ (B = Zr, Nb) [Zr and Nb doped europium titanate] utilizing various experimental techniques and theoretical calculations.

The cubic to tetragonal structural transition in pure EuTiO₃ is characterized by a pronounced step-like softening of the elastic moduli near 288 K [kelvin], which resembles …

Nanoscaled Cellulose And Its Carbonaceous Material: Application And Local Structure Investigation, Yujie Meng

Doctoral Dissertations

In this dissertation, cellulose nanocrystals three-dimensional morphology, size distribution, and the crystal structure were statistically and quantitatively investigated. Lognormal distribution was identified as the most likely for cellulose nanocrystals’ size distribution. Height and width dimensions were shown to decrease toward the ends from the midpoint of individual CNCs, implying a spindle-like shape. XRD analysis of crystallite size accompanied with TEM and AFM measurements revealed that the cross-sectional dimensions of individual switchgrass CNC were either rectangular or elliptical shape, with an approximately 3~5 nm [nanometer] lateral element length range. A sponge-like carbon aerogel from microfibril cellulose with high porosity, ultra-low density, …

Structural Characterizations Of Photo-Catalytic Titanium Oxide Nanoparticles Made From Amorphous Building Blocks, Mengkun Tian

Doctoral Dissertations

TiO₂ [titanium dioxide] nanoparticles (NPs) exhibit a variety of properties substantially departed from the optical and catalytic properties of the known bulk phases. A special interest in the engineering of functionality is how structures and bandgaps interact to enhance the photo-activity of TiO₂. However, fundamental understanding of bandgap-related changes is difficult at these length scales because of scarcity of methods capable of probing the bandgap and the structure of isolated small particles. In this research, we adopt a series of highly spatially resolved transmission electron microscopy (TEM) techniques to characterize the structures of amorphous TiO₂ nanoparticles …

Incipient Plasticity Of Metals And Alloys Using Nano-Indentation Technique, Dong Wu

Doctoral Dissertations

The incipient plasticity indicates the nucleation or activation of defects in materials and enables us to study the intrinsic mechanical properties of materials. In this dissertation, instrumented indentation technique was employed to study the incipient plasticity of metals (bcc-Cr, fcc-Ni, fcc-Au) and a fcc-structured high entropy alloy (HEA) NiFeCoMnCr. The critical shear stresses for pop-in in these materials were all within the range of theoretical strength of materials, indicating the nucleation of dislocations in perfect crystals.

In Chapter 3 and 4, indentation tests were conducted at elevated temperatures to study the pop-in behavior in bcc-Cr and fcc-Au. The pop-in load …

Development And Improvement Of Cerium Activated Gadolinium Gallium Aluminum Garnets Scintillators For Radiation Detectors By Codoping, Fang Meng

Doctoral Dissertations

Ce doped Gd3Ga3Al2O12 [gadolinium gallium aluminium oxides] is considered as a promising candidate for the next generation Positron Emission Tomography material due to its high light yield in theory. This dissertation is focused on studying the Gd3Ga3Al2O12:Ce crystals by codoping, aiming to improve the light yield and decay time experimentally and understand the underlying mechanism.

The work starts from prescreening appropriate codopants for Gd3Ga3Al2O12:Ce crystals. A cost-effective method is developed to predict the performance of the single crystals by characterizing the radioluminescence intensity and photoluminescence decay of the small polycrystalline pellets. This method is demonstrated by showing that the results …

Biodegradable Nano-Hybrid Polymer Composite Networks For Regulating Cellular Behavior, Charles Henley Sprague

Masters Theses

Photo-crosslinkable polymeric biomaterials have emerged in the field of biomedical research to promote tissue regeneration. For example, scaffolds that can be crosslinked and hardened in situ have been known to make suitable implant alternatives. Since injectable and photo-crosslinkable biomaterials offer the advantage of being minimally invasive, they have emerged to compete with autografts, a current highly invasive method to repair diseased tissue. A series of novel photo-crosslinkable, injectable, and biodegradable nano-hybrid polymers consisting of poly(ε-caprolactone fumarate) (PCLF) and polyhedral oligomeric silsesquioxane (POSS) has been synthesized in our laboratory via polycondensation. To engineer the material properties of the nano-hybrid networks, varied …

A High Pressure Cell For Spark Plasma Sintering, Justin Robert Carmichael

Masters Theses

Many nanostructured materials have been shown to have performance gains strongly dependent on the grain size in the material. Nanostructured thermoelectric materials for instance have found great performance increases through reduction of the grain sizes, due mostly to the scattering of phonons while retaining a good electrical conductivity. Other such examples abound where the grain size plays an important role in the performance of the material, including magnetic materials, proton fuel cell membranes, or simply improving the mechanical properties of a system through the Hall-Petch relationship.

A considerable amount of effort has been applied into reducing the grain size of …

Disorder In Mg1-Xnixal2o4 Spinel And Its Impact On The Response To Swift Heavy Ion Irradiation, Brandon Alexander Perlov

Masters Theses

Spinels, which are currently used in optical applications, have many proposed functions in the nuclear industry, such as a nuclear waste form due to its radiation resistance. Disordering plays a key role in the response of spinel to a wide range of irradiation conditions. The first part of this research project was on characterizing the type and degree of disorder that can be induced by chemical substitution in the magnesium nickel aluminate spinel solid solution series (Mg(1-x)Ni(x)Al2O4). Neutron total scattering has been used to characterize the structure at both the cation and anion sublattices. High-resolution pair distribution function analysis was …

Computational And Experimental Studies Of Ca12al14o33, Mayenite, Elijah Duncan Barlow

Masters Theses

In this study C₁₂Al₁₄O₃₃ [mayenite] is computationally modeled, synthesized, and compared to literature in order to build a knowledge base for the further study of this compound. It is hoped that this study of mayenite will lead to the development of a new transparent conductive oxide that uses earth abundant elements instead of rare earth elements. For this study polycrystalline mayenite was synthesized using traditional solid-state synthesis techniques, and growth of a single crystal was then attempted. The VASP software package was then used to simulate the compound, both physically and electronically. The results of the simulation were then compared …

Mixing Metals For Magic Materials: Analysis Of Binary Eutectic Alloys For Metamaterial Applications, Ethan Elder Fox

Masters Theses

Uses of metamaterials, also known as negative index materials (NIMs), are wide ranging and include lenses that have a resolution beyond the diffraction limit, incredibly small antenna, and cloaking devices for optical, infrared, and microwave wavelengths.

The unique properties of metamaterials are not found in any naturally occurring material. By having simultaneously negative values for ε [electrical permittivity] and μ [magnetic permeability], a metamaterial can have a negative index of refraction over a certain frequency band. The unique properties of negative index materials emerge chiefly from their highly ordered structure.

Binary eutectic alloys have the potential to be used as …

The Experimental And Theoretical Study Of Plasticity Improvement Of Zr-Based Bulk Metallic Glasses, Xie Xie

Doctoral Dissertations

Bulk metallic glasses (BMGs) attract more and more attention for their great mechanical properties, such as high strength, good corrosion resistance, etc. However, even though extensive studies have been made, their deformation mechanisms are still not well understood. Their limited plasticity and catastrophic failure after yielding severely prevent their broad applications in industry and daily life. To improve their plasticity, some work has been done through miscellaneous processing methods, e.g., thin-film coating, surface treatment, and ion irradiation. The present work also focuses on the plastic deformation of BMGs, and is expected to deepen the fundamental understanding of the deformation mechanisms …

Bulk Heterojunctions In Photovoltaic Devices, Ondrej Edward Dyck

Doctoral Dissertations

Current solar cells, on the market today, have little room for improved efficiency or cost reduction. Part of this is due to the costly manufacture of high purity silicon and the current fabrication methods for solar cells. Solution processable solar cells would mark a great stride forward to cost reduction. If such cells can be demonstrated to be efficient enough and stable enough it would be a turning point in history. However, solution processable devices still need much work before they can compete in the market. This text addresses characterization problems in the TEM, covers a study dealing with optimization …

3d Kinematic And Strength Behavior Of Granular Materials At The Particle-Level, Mehmet Burak Cil

Doctoral Dissertations

The macro-scale behavior of uncemented granular materials is governed by the particle-to-particle interactions. Therefore, accurate assessment of the micro-scale mechanics is essential for better understanding of the fundamental behavior of granular materials. Particle fracture phenomenon and force transmission mechanisms in natural granular assemblies such as sands have not been fully understood due to the lack of micro-scale experimental measurements. The objective of this dissertation is to provide key quantitative measurements about these issues using powerful non-destructive experimental 3D x-ray diffraction (3DXRD) and synchrotron micro-tomography (SMT) techniques, as well as distinct element method (DEM). 3DXRD was employed to measure the volume-averaged …

Engineering The “Pluripotency” Of Zr-Based Bulk Metallic Glasses As Biomedical Materials, Lu Huang

Doctoral Dissertations

Bulk metallic glasses (BMGs) are a family of novel alloys with amorphous microstructures. The combination of their excellent mechanical properties, good chemical stability, high thermal formability, and general biocompatibility has brought up new opportunities for biomaterials. Research in this dissertation was focused on exploring multiple biomedical functionalities of Zr-based BMGs over a wide spectrum, combining materials and biological characterizations, through experimental and computational approaches. Four distinct yet interconnected tasks were endeavored, involving inflammation, hard-tissue implant, soft-tissue prosthesis, and pathogenic infection.

The inflammation that can be potentially triggered by Zr-based BMGs was investigated using macrophages. Lower level or comparable macrophage activations …

Discovery And Improvement Of Novel Metal Halide Scintillators For Radiation Detection Applications, Hua Wei

Doctoral Dissertations

Scintillation materials are in great demand for radiation detection applications. In this dissertation work, a series of new metal halide scintillation materials are presented. A comprehensive procedure of candidate scintillator screening, single crystal growth, scintillation properties characterizations, and scintillation mechanism investigations are established. The potential candidate materials are firstly synthesized by melt-freeze method to form polycrystalline. The scintillation properties of the polycrystalline specimen are characterized to select the most promising scintillators. The selected scintillators are grown into single crystals. Protocols including raw materials purification, materials pre-mixing, ampoule design, and furnace manipulation are developed to improve the scintillators’ performance.

Cerium-doped ternary …

Electronic Energy Loss Of Heavy Ions And Its Effects In Ceramics, Ke Jin

Doctoral Dissertations

Energy loss of medium energy heavy ions (i.e. Cl, Br, I, and Au) in thin compound foils containing light elements (i.e. silicon carbide and silicon dioxide) is directly measured using a time-of-flight elastic recoil detection analysis (ToF-ERDA) technique. An improved data analysis procedure is proposed to provide the experimentally determined electronic stopping powers. This analysis procedure requires reliable predictions of nuclear stopping. Thus, the nuclear stopping predicted by the Stopping and Range of Ions in Matter (SRIM) code is validated by measuring the angular distribution of 1 MeV Au ions after penetrating a thin silicon nitride foil, using a secondary …

Studies Of Strongly Correlated Electron Systems Using Neutron Scattering, Yuen Yiu

Doctoral Dissertations

The world presents many natural and man-made crises and challenges that require scientific solutions. Condensed matter physics is one of the most influential and solution oriented disciplines in science. The field saw a significant rise in popularity especially during the past century as mankind enters the Information Age, when energy and computing related technologies become ubiquitous. This technological progress has been driven by efforts from scientists and engineers, through the synthesis, understanding, and implementation of new materials. Condensed matter physicists strive to solve puzzles at the frontier of material research. In the 21st century we have many advance tools at …

Development And Demonstration Of Critical Components Of Aluminum Based Energy Storage Devices Using The Chloroaluminate Ionic Liquids, Mengqi Zhang

Doctoral Dissertations

This dissertation considers the development of porous carbon materials as the substrates for Al deposition/dissolution in an Al based ionic liquid flow battery (ILFB) and demonstration of an Al based hybrid supercapacitor. The Aluminum chloride/ 1-ethyl-3-methylimidazolium chloride chloroaluminate ionic liquid is utilized as the electrolyte for these Al based energy storage devices. The ILFB has less capital cost than the all-vanadium redox flow battery because of the inexpensive AlCl₃. The feasibility to equip a tank of solid aluminum chloride in an ILFB system aiming to improve energy density is investigated. A critical range of temperature data (50-130 celsius …

Structural Aspects Of Deformation In Bulk Metallic Glasses, Yang Tong

Doctoral Dissertations

Metallic glasses have liquid-like structure without well-defined topological defects like dislocations in metals and alloys. The unique disordered structure of metallic glasses leads to unique mechanical properties, such as inhomogeneous deformation at low temperature and homogeneous deformation at high temperature, and brittle behavior induced by annealing. This dissertation address three critical issues related to the mechanical behavior of metallic glasses:

1. Identification of deformation defects in metallic glasses. We have conducted high energy X-ray diffraction experiment — using anisotropic pair distribution function — to characterize the size and density of defects in metallic glasses activated by external stresses. Our results based …

Microstructures And Mechanical Behavior Of Nial-Strengthened Ferritic Alloys At Room And Elevated Temperatures, Zhiqian Sun

Doctoral Dissertations

In order to improve the thermal efficiency and decrease the greenhouse gases emission, it is required to increase the steam temperature and pressure in fossil-energy power plants. In the United States, research has been performing in order to push steam temperature to 760 Celsius degree and steam pressure to 35 MPa. However, the highest operational temperature for current commercial heat-resistant ferritic steels is ~ 620 Celsius degree. In this sense, new advanced ferritic alloys with better creep resistance are needed, considering such service conditions in next-generation ultra-supercritical fossil-energy power plants.

Coherent B2-ordered NiAl-type precipitates have been employed to reinforce the …