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Defect Behaviors in Zinc Oxide and Zinc Titanates Ceramics from First Principles Computer Simulations
ZnO and ZnO-TiO2 ceramics have intriguing electronic and mechanical properties and find applications in many fields. Many of these properties and applications rely on the understanding of defects and defect processes in these oxides as these defects control the electronic, catalytic and mechanical behaviors. The goal of this dissertation is to systematically study the defects and defects behaviors in Wurtzite ZnO and Ilmenite ZnTiO3 by using first principles calculations and classical simulations employing empirical potentials. Firstly, the behavior of intrinsic and extrinsic point defects in ZnO and ZnTiO3 ceramics were investigated. Secondly, the effect of different surface absorbents and surface defects on the workfunction of ZnO were studied using DFT calculations. The results show that increasing the surface coverage of hydrocarbons decreased the workfunction. Lastly, the stacking fault behaviors on ilmenite ZnTiO3 were investigated by calculating the Generalized Stacking Fault (GSF) energies using density functional theory based first principles calculations and classical calculations employing effective partial charge inter-atomic potentials. The gamma-surfaces of two low energy surfaces, (110) and (104), of ZnTiO3 were fully mapped and, together with other analysis such as ideal shear stress calculations.
The Role of Misfit Strain and Oxygen Content on Formation and Evolution of Omega Precipitate in Metastable Beta-titanium Alloys
β-Ti alloys are widely used in airframe and biomedical applications due to their high ductility, high hardenability, and low elastic modulus. The phase transformations in β-Ti alloys are rather complex due to formation of metastable phases during various thermo-mechanical treatments. One such critical metastable phase, the hexagonal omega (ω) phase, can form in β-Ti alloys under quenching from the high temperature β phase and/or isothermal aging at intermediate temperature. Despite a substantial amount of reported works on the ω phase, there are several critical issues related to the ω formation need to be resolved, e.g. role of alloying elements and oxygen content. Therefore, this dissertation has attempted to provide insights into ω transformation in low misfit (Ti-Mo) and high misfit (Ti-V) binary systems as well as multicomponent (Ti-Nb-Zr-Ta) alloys. The evolution of ω structure, morphology and composition from the early stage (β-solution+quenched) to later stages after prolonged aging are systematically investigated by coupling transmission electron microscopy (TEM), atom probe tomography (APT) and high-energy synchrotron X-ray diffraction techniques. The influence of aging temperature and duration on characteristic of ω phase in Ti-Mo, and Ti-V alloys is addressed in details. It is found that compositional changes during aging can alter the structure, size and morphology of ω precipitates. In low misfit alloys, the ellipsoidal morphology of ω phase was retained during isothermal aging, while in high misfit alloys it changed from ellipsoidal to cuboidal morphology after prolonged aging. Secondly, ω transformation in biomedical Ti-Nb-Zr-Ta alloy is probed in which the micro-hardness was sensitive to microstructural changes. Furthermore, the evolution of oxygen concentration in ω precipitates during various aging conditions in binary Ti-Mo and Ti-V alloys are reported. It has been accepted that interstitial elements such as oxygen can largely alter mechanical behavior and the microstructure of Ti-alloys. Recently, oxygen is intentionally added ...
Angular Analysis of a Wide-Band Energy Harvester based on Mutually Perpendicular Vibrating Piezoelectric Beams
The recent advancements in electronics and the advents of small scaled instruments has increased the attachment of life and functionality of devices to electrical power sources but at the same time granted the engineers and companies the ability to use smaller sources of power and batteries. Therefore, many scientists have tried to come up with new solutions for a power alternatives. Piezoelectric is a promising material which can readily produce continuous electric power from mechanical inputs. However, their power output is dependent upon several factors such as, system natural frequency, their position in the system, the direction of vibration and many other internal and external factors. In this research the working bandwidth of the system is increased through utilizing of two different piezoelectric beam in different directions. The dependency of output power with respect to rotation angle and also the frequency shift due to the rotation angle is studied.
Improving the Long-term Performance of PVC Compositions
PVC are extensively applied in many fields, such as cables, pipes, vehicles, shoes, toys and infusion bags. Generally, plasticizers are blended with PVC to improve the ability of process in industrial production; however, the toxic plasticizers will gradually migrate to the surface of products and such a leakage results in brittleness of plasticized PVC and environmental pollution. In other words, humans are frequently exposed to the potential risks. According to previous researches, cross-linked PVC was proved that it was able to hinder the migration of plasticizer. Thus, in this research, we selected some commercially used cross-linking agents and employed six different tests based on mechanical, tribological and microscopy analysis in order to seek the best solution against plasticizer migration. Thus, we expected to develop a cross-linked flexible PVC which performed improved long-term performance and extended lifetime.
Sliding Friction and Wear Behavior of High Entropy Alloys at Room and Elevated Temperatures
Structure-tribological property relations have been studied for five high entropy alloys (HEAs). Microhardness, room and elevated (100°C and 300°C) temperature sliding friction coefficients and wear rates were determined for five HEAs: Co0.5 Cr Cu0.5 Fe Ni1.5 Al Ti0.4; Co Cr Fe Ni Al0.25 Ti0.75; Ti V Nb Cr Al; Al0.3CoCrFeNi; and Al0.3CuCrFeNi2. Wear surfaces were characterized with scanning electron microscopy and micro-Raman spectroscopy to determine the wear mechanisms and tribochemical phases, respectively. It was determined that the two HEAs Co0.5 Cr Cu0.5 Fe Ni1.5 Al Ti0.4 and Ti V Nb Cr Al exhibit an excellent balance of high hardness, low friction coefficients and wear rates compared to 440C stainless steel, a currently used bearing steel. This was attributed to their more ductile body centered cubic (BCC) solid solution phase along with the formation of tribochemical Cr oxide and Nb oxide phases, respectively, in the wear surfaces. This study provides guidelines for fabricating novel, low-friction, and wear-resistant HEAs for potential use at room and elevated temperatures, which will help reduce energy and material losses in friction and wear applications.
Design and Manufacture of Molding Compounds for High Reliability Microelectronics in Extreme Conditions
The widespread use of electronics in more avenues of consumer use is increasing. Applications range from medical instrumentation that directly can affect someone's life, down hole sensors for oil and gas, aerospace, aeronautics, and automotive electronics. The increased power density and harsh environment makes the reliability of the packaging a vital part of the reliability of the device. The increased importance of analog devices in these applications, their high voltage and high temperature resilience is resulting in challenges that have not been dealt with before. In particular packaging where insulative properties are vital use polymer resins modified by ceramic fillers. The distinct dielectric properties of the resin and the filler result in charge storage and release of the polarization currents in the composite that have had unpredictable consequences on reliability. The objective of this effort is therefore to investigate a technique that can be used to measure the polarization in filled polymer resins and evaluate reliable molding compounds. A valuable approach to measure polarization in polymers where charge release is tied to the glass transition in the polymer is referred to as thermally stimulated depolarization current (TSDC) technique. In this dissertation a new TSDC measurement system was designed and fabricated. The instrument is an assembly of several components that are automated via a LabVIEW program that gives the user flexibility to test different dielectric compounds at high temperatures and high voltage. The temperature control is enabled through the use of dry air convection heating at a very slow rate enabling controlled heating and cooling. Charge trapping and de-trapping processes were investigated in order to obtain information on insulating polymeric composites and how to optimize it. A number of material properties were investigated. First, polarization due to charges on the filer were investigated using composites containing charged and uncharged particles using ...
Compostable Soy-Based Polyurethane Foam with Kenaf Core Modifiers
Building waste and disposable packaging are a major component in today's landfills. Most of these are structural or thermally insulative polymer foams that do not degrade over a long period of time. Currently, there is a push to replace these foams with thermoplastic or biodegradable foams that can either be recycled or composted. We propose the use of compostable soy-based polyurethane foams (PU) with kenaf core modifiers that will offer the desired properties with the ability to choose responsible end-of-life decisions. The effect of fillers is a critical parameter in investigating the thermal and mechanical properties along with its effect on biodegradability. In this work, foams with 5%, 10%, and 15% kenaf core content were created. Two manufacturing approaches were used: the free foaming used by spray techniques and the constrained expansion complementary to a mold cavity. Structure-property relations were examined using differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), thermal conductivity, compression values, scanning electron microscopy (SEM), x-ray micro-computed tomography (micro-CT), and automated multiunit composting system (AMCS). The results show that mechanical properties are reduced with the introduction of kenaf core reinforcement while thermal conductivity and biodegradability display a noticeable improvement. This shows that in application properties can be improved while establishing a responsible end-of-life choice.
Friction Stir Welding of High Strength Precipitation Strengthened Aluminum Alloys
Rising demand for improved fuel economy and structural efficiency are the key factors for use of aluminum alloys for light weighting in aerospace industries. Precipitation strengthened 2XXX and 7XXX aluminum alloys are the key aluminum alloys used extensively in aerospace industry. Welding and joining is the critical step in manufacturing of integrated structures. Joining of precipitation strengthened aluminum alloys using conventional fusion welding techniques is difficult and rather undesirable in as it produces dendritic microstructure and porosities which can undermine the structural integrity of weldments. Friction stir welding, invented in 1991, is a solid state joining technique inherently benefitted to reduces the possibility of common defects associated with fusion based welding techniques. Weldability of various 2XXX and 7XXX aluminum alloys via friction stir welding was investigated. Microstructural and mechanical property evolution during welding and after post weld heat treatment was studied using experimental techniques such as transmission electron microscopy, differential scanning calorimetry, hardness testing, and tensile testing. Various factors such as peak welding temperature, cooling rate, external cooling methods (thermal management) which affects the strength of the weldment were studied. Post weld heat treatment of AL-Mg-Li alloy produced joint as strong as the parent material. Modified post weld heat treatment in case of welding of Al-Zn-Mg alloy also resulted in near 100% joint efficiency whereas the maximum weld strength achieved in case of welds of Al-Cu-Li alloys was around 80-85% of parent material strength. Low dislocation density and high nucleation barrier for the precipitates was observed to be responsible for relatively low strength recovery in Al-Cu-Li alloys as compared to Al-Mg-Li and Al-Zn-Mg alloys.
Microstructure for Enhanced Plasticity and Toughness
Magnesium is the lightest metal with a very high specific strength. However, its practical applicability is limited by its toughness and reliability. Mg, being HCP has low ductility. This makes the improvement of toughness a grand challenge in Mg alloys. Friction stir processing (FSP) is a thermomechanical technique used to effect microstructural modification. Here, FSP was utilized to affect the toughness of WE43 sheets through microstructural modification. Room temperature Kahn-type tests were conducted to measure the toughness of WE43 sheets. Microscopic techniques (SEM, TEM) was utilized to study the effect of various microstructural factors like grain size, texture, constituent particles, precipitates on crack initiation and propagation. Tensile properties were evaluated by mini-tensile tests. Crack growth in WE43 sheets was also affected by mechanics and digital image correlation (DIC) was utilized to study the plastic zone size. The underlying mechanisms affecting toughness of these sheets were understood which will help in formulating ways in improving it. WE43 nanocomposites were fabricated via FSP. Uniform distribution of reinforcements was obtained in the composites. Improved mechanical properties like that of enhanced strength, increased hardness and stiffness were obtained. But contrary to other metal matrix composites which show reduction in ductility with incorporation of ceramic reinforcements, the nanocomposites showed good strength-ductility combination. The composites were precisely characterized and mechanisms governing this property were studied. The nano-length of the reinforcements was observed to be the main criteria and the dislocation-particle interaction, the main reason behind the strength-ductility property.
Workfunction tuning of AZO Films Through Surface Modification for Anode Application in OLEDs.
Widespread use of organic light emitting diodes (OLEDs) in solid state lighting and display technologies require efficiency and lifetime improvements, as well as cost reductions, inclusive of the transparent conducting oxide (TCO). Indium tin oxide (ITO) is the standard TCO anode in OLEDs, but indium is expensive and the Earth's reserve of this element is limited. Zinc oxide (ZnO) and its variants such as aluminum-doped ZnO (AZO) exhibit comparable electrical conductivity and transmissivity to ITO, and are of interest for TCO applications. However, the workfunction of ZnO and AZO is smaller compared to ITO. The smaller workfunction of AZO results in a higher hole injection barrier at the anode/organic interface, and methods of tuning its workfunction are required. This dissertation tested the hypothesis that workfunction tuning of AZO films could be achieved by surface modification with electronegative oxygen and fluorine plasmas, or, via use of nanoscale transition metal oxide layers (MoOx, VOx and WOx). Extensive UPS, XPS and optical spectroscopy studies indicate that O2 and CFx plasma treatment results in an electronegative surface, surface charge redistribution, and a surface dipole moment which reinforces the original surface dipole leading to workfunction increases. Donor-like gap states associated with partially occupied d-bands due to non-stoichiometry determine the effective increased workfunction of the AZO/transition-metal oxide stacks. Reduced hole injection barriers were engineered by ensuring that the surface ad-layers were sufficiently thin to facilitate Fowler-Nordheim tunneling. Improved band alignments resulted in improved hole injection from the surface modified AZO anodes, as demonstrated by I-V characterization of hole only structures. Energy band alignments are proposed based on the aforementioned spectroscopies. Simple bilayer OLEDs employing the surface modified AZO anodes were fabricated and characterized to compare their performance with standard ITO. Anodes consisting of AZO with MoOx or VOx interfacial layers exhibited 50% and 71% improvement in ...
Friction Stir Welding of Precipitation Strengthened Aluminum 7449 Alloys
The Al-Zn-Mg-Cu (7XXX series) alloys are amongst the strongest aluminum available. However, they are considered unweldable with conventional fusion techniques due to the negative effects that arise with conventional welding, including hydrogen porosity, hot cracking, and stress corrosion cracking. For this reason, friction stir welding has emerged as the preferred technique to weld 7XXX series alloys. Aluminum 7449 is one of the highest strength 7XXX series aluminum alloy. This is due to its higher zinc content, which leads to a higher volume fraction of eta' precipitates. It is typically used in a slight overaged condition since it exhibits better corrosion resistance. In this work, the welds of friction stir welded aluminum 7449 were studied extensively. Specific focus was placed in the heat affected zone (HAZ) and nugget. Thermocouples were used in the heat affected zone for three different depths to obtain thermal profiles as well as cooling/heating profiles. Vicker microhardness testing, transmission electron microscope (TEM), and differential scanning calorimeter (DSC) were used to characterize the welds. Two different tempers of the alloy were used, a low overaged temper and a high overaged temper. A thorough comparison of the two different tempers was done. It was found that highly overaged aluminum 7449 tempers show better properties for friction stir welding. A heat gradient along with a high conducting plate (Cu) used at the bottom of the run, resulted in welds with two separate microstructures in the nugget. Due to the microstructure at the bottom of the nugget, higher strength than the base metal is observed. Furthermore, the effects of natural aging and artificial aging were studied to understand re-precipitation. Large improvements in strength are observed after natural aging throughout the welds, including improvements in the HAZ.
In Vitro Behavior of AZ31B Mg-Hydroxyapatite Metallic Matrix Composite Surface Fabricated via Friction Stir Processing
Magnesium and its alloys have been considered for load-bearing implant materials due to their similar mechanical properties to the natural bone, excellent biocompatibility, good bioactivity, and biodegradation. Nevertheless, the uncontrollable corrosion rate in biological environment restrains their application. Hydroxyapatite (HA, Ca10(PO4)6(OH)2) is a widely used bio-ceramic which has bone-like mineral structure for bone fixation. Poor fracture toughness of HA makes it not suitable for load-bearing application as a bulk. Thus, HA is introduced into metallic surface in various forms for improving biocompatibility. Recently friction stir processing (FSP) has emerged as a surface modification tool for surface/substrate grain refinement and homogenization of microstructure in biomaterial. In the pressent efforts, Mg-nHA composite surface on with 5-20 wt% HA on Mg substrate were fabricated by FSP for biodegradation and bioactivity study. The results of electrochemical measurement indicated that lower amount (~5% wt%) of Ca in Mg matrix can enhance surface localized corrosion resistance. The effects of microstructure,the presence of HA particle and Mg-Ca intermetallic phase precipitates on in vitro behavior of Mg alloy were investigated by TEM, SEM, EDX,XRD ,and XPS. The detailed observations will be discussed during presentation.
Influence of High Strain Rate Compression on Microstructure and Phase Transformation of NiTi Shape Memory Alloys
Since NiTi shape memory alloy (SMA) was discovered in the early 1960s, great progress has been made in understanding the properties and mechanisms of NiTi SMA and in developing associated products. For several decades, most of the scientific research and industrial interests on NiTi SMA has focused on its superelastic applications in the biomedical field and shape memory based “smart” devices, which involves the low strain rate (around 0.001 s^-1) response of NiTi SMA. Due to either stress-induced martensite phase transformation or stress induced martensite variant reorientation under the applied load, NiTi SMA has exhibited a high damping capacity in both austenitic and martensitic phase. Recently, there has been an increasing interest in exploitation of the high damping capacity of NiTi SMA to develop high strain rate related applications such as seismic damping elements and energy absorbing devices. However, a systematic study on the influence of strain, strain rate and temperature on the mechanical properties, phase transformation, microstructure and crystal structure is still limited, which leads to the difficulties in the design of products being subjected to high strain rate loading conditions. The four main objectives of the current research are: (1) achieve the single loading and the control of strain, constant strain rate and temperature in high strain rate compression tests of NiTi SMA specimens using Kolsky (split Hopkinson) compression bar; (2) explore the high strain rate compressive responses of NiTi SMA specimens as a function of strain (1.4%, 1.8%, 3.0%, 4.8%, and 9.6%), strain rate (400, 800 and 1200 s^-1), and temperature (room temperature (294 K) and 373 K); (3) characterize and compare the microstructure, phase transformation and crystal structure of NiTi SMAs before and after high strain rate compression; and (4) correlate high strain rate deformation with the changes of microstructure, phase transformation characteristics and crystal structure. ...
Fatigue Behavior of A356 Aluminum Alloy
Metal fatigue is a recurring problem for metallurgists and materials engineers, especially in structural applications. It has been responsible for many disastrous accidents and tragedies in history. Understanding the micro-mechanisms during cyclic deformation and combating fatigue failure has remained a grand challenge. Environmental effects, like temperature or a corrosive medium, further worsen and complicate the problem. Ultimate design against fatigue must come from a materials perspective with a fundamental understanding of the interaction of microstructural features with dislocations, under the influence of stress, temperature, and other factors. This research endeavors to contribute to the current understanding of the fatigue failure mechanisms. Cast aluminum alloys are susceptible to fatigue failure due to the presence of defects in the microstructure like casting porosities, non-metallic inclusions, non-uniform distribution of secondary phases, etc. Friction stir processing (FSP), an emerging solid state processing technique, is an effective tool to refine and homogenize the cast microstructure of an alloy. In this work, the effect of FSP on the microstructure of an A356 cast aluminum alloy, and the resulting effect on its tensile and fatigue behavior have been studied. The main focus is on crack initiation and propagation mechanisms, and how stage I and stage II cracks interact with the different microstructural features. Three unique microstructural conditions have been tested for fatigue performance at room temperature, 150 °C and 200 °C. Detailed fractography has been performed using optical microscopy, scanning electron microscopy (SEM) and electron back scattered diffraction (EBSD). These tools have also been utilized to characterize microstructural aspects like grain size, eutectic silicon particle size and distribution. Cyclic deformation at low temperatures is very sensitive to the microstructural distribution in this alloy. The findings from the room temperature fatigue tests highlight the important role played by persistent slip bands (PSBs) in fatigue crack initiation. At room ...
Stable Nanocrystalline Au Film Structures for Sliding Electrical Contacts
Hard gold thin films and coatings are widely used in electronics as an effective material to reduce the friction and wear of relatively less expensive electrically conductive materials while simultaneously seeking to provide oxidation resistance and stable sliding electrical contact resistance (ECR). The main focus of this dissertation was to synthesize nanocrystalline Au films with grain structures capable of remaining stable during thermal exposure and under sliding electrical contact stress and the passing of electrical current. Here we have utilized a physical vapor deposition (PVD) technique, electron beam evaporation, to synthesize Au films modified by ion implantation and codeposited ZnO hardened Au nanocomposites. Simultaneous friction and ECR experiments of low fluence (< 1x10^17 cm^-2) He and Ar ion implanted Au films showed reduction in friction coefficients from ~1.5 to ~0.5 and specific wear rates from ~4x10^-3 to ~6x10^-5 mm^3/N·m versus as-deposited Au films without significant change in sliding ECR (~16 mΩ). Subsurface microstructural changes of He implanted films due to tribological stress were analyzed via site-specific cross-sectional transmission electron microscopy (TEM) and revealed the formation of nanocrystalline grains for low energy (22.5 keV) implantation conditions as well as the growth and redistribution of cavities. Nanoindentation hardness results revealed an increase from 0.84 GPa for as-deposited Au to ~1.77 GPa for Au uniformly implanted with 1 at% He. These strength increases are correlated with an Orowan hardening mechanism that increases proportionally to (He concentration)1/3. Au-ZnO nanocomposite films in the oxide dilute regime (< 5 vol% ZnO) were investigated for low temperature aging stability in friction and ECR. Annealing at 250 °C for 24 hours Au-(2 vol%)ZnO retained a friction coefficient comparable to commercial Ni hardened Au of ~ 0.3 and sliding ECR values of ~35 mΩ. Nanoindentation hardness increases of these films (~2.6 GPa for 5 vol% ZnO) are correlated to ...
Microstructural Phase Evolution In Laser Deposited Compositionally Graded Titanium-Chromium Alloys
A compositionally graded Ti-xCr (10≤x≤30 wt%) alloy has been fabricated using Laser Engineered Net Shaping (LENSTM) to study the microstructural phase evolution along a compositional gradient in both as-deposited and heat treated conditions (1000°C followed by furnace cooling or air cooling). The alloys were characterized by SEM BSE imaging, XRD, EBSD, TEM and micro-hardness measurements to determine processing-structure-property relations. For the as-deposited alloy, α-Ti, β-Ti, and TiCr2 (C15 Laves) phases exist in varying phase fractions, which were influential in determining hardness values. With the furnace cooled alloy, there was more homogeneous nucleation of α phase throughout the sample with a larger phase fraction of TiCr2 resulting in increased hardness values. When compared to the air cooled alloy, there was absence of wide scale nucleation of α phase and formation of ω phase within the β phase due to the quicker cooling from elevated temperature. At lower concentrations of Cr, the kinetics resulted in a diffusionless phase transformation of ω phase with increased hardness and a lower phase fraction of TiCr2. In contrast at higher Cr concentrations, α phase separation reaction occurs where the β phase is spinodally decomposed to Cr solute-lean β1 and solute-rich β2 resulting in reduced hardness.
Reactions and Interfacial Behaviors of the Water–Amorphous Silica System from Classical and Ab Initio Molecular Dynamics Simulations
Due to the wide application of silica based systems ranging from microelectronics to nuclear waste disposal, detailed knowledge of water-silica interactions plays an important role in understanding fundamental processes, such as glass corrosion and the long term reliability of devices. In this dissertation, atomistic computer simulation methods have been used to explore and identify the mechanisms of water-silica reactions and the detailed processes that control the properties of the water-silica interfaces due to their ability to provide atomic level details of the structure and reaction pathways. The main challenges of the amorphous nature of the silica based systems and nano-porosity of the structures were overcome by a combination of simulation methodologies based on classical molecular dynamics (MD) simulations with Reactive Force Field (ReaxFF) and density functional theory (DFT) based ab initio MD simulations. Through the development of nanoporous amorphous silica structure models, the interactions between water and the complex unhydroxylated internal surfaces identified the unusual stability of strained siloxane bonds in high energy ring structure defects, as well as the hydroxylation reaction kinetics, which suggests the difficulty in using DFT methods to simulate Si-O bond breakage with reasonable efficiency. Another important problem addressed is the development of silica gel structures and their interfaces, which is considered to control the long term residual dissolution rate in borosilicate glasses. Through application of the ReaxFF classical MD potential, silica gel structures which mimic the development of interfacial layers during silica dissolution were created A structural model, consisting of dense silica, silica gel, and bulk water, and the related interfaces was generated, to represent the dissolution gel structure. High temperature evolution of the silica-gel-water (SGW) structure was performed through classical MD simulation of the system, and growth of the gel into the water region occurred, as well as the formation of intermediate range structural ...
Enhancement of Light Emission from Metal Nanoparticles Embedded Graphene Oxide
A fully oxidized state of graphene behaves as a pure insulating while a pristine graphene behaves as a pure conducting. The in-between oxide state in graphene which is the controlled state of oxide behaves as a semiconducting. This is the key condition for tuning optical band gap for the better light emitting property. The controlling method of oxide in graphene structure is known as reduction which is the mixed state of sp2 and sp3 hybrid state in graphene structure. sp2 hybridized domains correspond to pure carbon-carbon bond i.e. pristine graphene while sp3 hybridized domains correspond to the oxide bond with carbon i.e. defect in graphene structure. This is the uniqueness of the graphene-base material. Graphene is a gapless material i.e. having no bandgap energy and this property prevents it from switching device applications and also from the optoelectronic devices applications. The main challenge for this material is to tune as a semiconducting which can open the optical characteristics and emit light of desired color. There may be several possibilities for the modification of graphene-base material that can tune a band gap. One way is to find semiconducting property by doping the defects into pristine graphene structure. Other way is oxides functional groups in graphene structure behaves as defects. The physical properties of graphene depend on the amount of oxides present in graphene structure. So if there are more oxides in graphene structure then this material behaves as a insulating. By any means if it can be reduced then oxides amount to achieve specific proportion of sp2 and sp3 that can emit light of desired color. Further, after achieving light emission from graphene base material, there is more possibility for the study of non-linear optical property. In this work, plasmonic effect in graphene oxide has been focused. Mainly there are two ...
Thermomechanical Processing, Additive Manufacturing and Alloy Design of High Strength Mg Alloys
The recent emphasis on magnesium alloys can be appreciated by following the research push from several agencies, universities and editorial efforts. With a density equal to two-thirds of Al and one-thirds of steel, Mg provides the best opportunity for lightweighting of metallic components. However, one key bottleneck restricting its insertion into industrial applications is low strength values. In this respect, Mg-Y-Nd alloys have been promising due to their ability to form strengthening precipitates on the prismatic plane. However, if the strength is compared to Al alloys, these alloys are not attractive. The primary reason for low structural performance in Mg is related to low alloying and microstructural efficiency. In this dissertation, these terminologies are discussed in detail. A simple calculation showed that the microstructural efficiency in Mg-4Y-3Nd alloy is 30% of its maximum potential. Guided by the definitions of alloying and microstructural efficiency, the two prime objectives of this thesis were to: (i) to use thermomechanical processing routes to tailor the microstructure and achieve high strength in an Mg-4Y-3Nd alloy, and (ii) optimize the alloy chemistry of the Mg-rare earth alloy and design a novel rare—earth free Mg alloy by Calphad approach to achieve a strength of 500 MPa. Experimental, theoretical and computational approaches have been used to establish the process-structure-property relationships in an Mg-4Y-3Nd alloy. For example, increase in strength was observed after post aging of the friction stir processed/additive manufactured microstructure. This was attributed to the dissolution of Mg2Y particles which increased the alloying and microstructural efficiency. Further quantification by numerical modeling showed that the effective diffusivity during friction stir processing and friction stir welding is 60 times faster than in the absence of concurrent deformation leading to the dissolution of thermally stable particles. In addition, the investigation on the interaction between dislocations and strengthening precipitate revealed that, ...
Synchrotron Radiation X-Ray Diffraction of Nickel-Titanium Shape Memory Alloy Wires during Mechanical Deformation
Shape memory alloys (SMAs) are a new generation material which exhibits unique nonlinear deformations due to a phase transformation which allows it to return to its original shape after removal of stress or a change in temperature. It shows a shape memory effect (martensitic condition) and pseudoelasticity (austenitic condition) properties depends on various heat treatment conditions. The reason for these properties depends on phase transformation through temperature changes or applied stress. Many technological applications of austenite SMAs involve cyclical mechanical loading and unloading in order to take advantage of pseudoelasticity, but are limited due to poor fatigue life. In this thesis, I investigated two important mechanical feature to fatigue behavior in pseudoelastic NiTi SMA wires using high energy synchrotron radiation X-ray diffraction (SR-XRD). The first of these involved simple bending and the second of these involved relaxation during compression loading. Differential scanning calorimetry (DSC) was performed to identify the phase transformation temperatures. Scanning electron microscopy (SEM) images were collected for the initial condition of the NiTi SMA wires and during simple bending, SEM revealed that micro-cracks in compression regions of the wire propagate with increasing bend angle, while tensile regions tend to not exhibit crack propagation. SR-XRD patterns were analyzed to study the phase transformation and investigate micromechanical properties. By observing the various diffraction peaks such as the austenite (200) and the martensite (100), (110), and (101) planes, intensities and residual strain values exhibit strong anisotropy depending upon whether the sample is in compression or tension during simple bending. This research provides insight into two specific mechanical features in pseudoelastic NiTi SMA wires.
Deformation Micro-mechanisms of Simple and Complex Concentrated Fcc Alloys
The principal objective of this work was to elucidate the effect of microstructural features on the intrinsic dislocation mechanisms in two FCC alloys. First alloy Al0.1CoCrFeNi was from a new class of material known as complex concentrated alloys, particularly high entropy alloys (HEA). The second was a conventional Al-Mg-Sc alloy in ultrafine-grained (UFG) condition. In the case of HEA, the lattice possess significant lattice strain due to the atomic size variation and cohesive energy differences. Moreover, both the lattice friction stress and the Peierls barrier height are significantly larger than the conventional FCC metals and alloys. The experimental evidences, so far, provide a distinctive identity to the nature and motion of dislocations in FCC HEA as compared to the conventional FCC metals and alloys. Hence, the thermally activated dislocation mechanisms and kinetics in HEA has been studied in detail. To achieve the aim of examining the dislocation kinetics, transient tests, both strain rate jump tests and stress relaxation tests, were conducted. Anomalous behavior in dislocation kinetics was observed. Surprisingly, a large rate sensitivity of the flow stress and low activation volume of dislocations were observed, which are unparalleled as compared to conventional CG FCC metals and alloys. The observed trend has been explained in terms of the lattice distortion and dislocation energy framework. As opposed to the constant dislocation line energy and Peierls potential energy (amplitude, ΔE) in conventional metals and alloys, both line energy and Peierls potential undergo continuous variation in the case of HEA. These energy fluctuations have greatly affected the dislocation mobility and can be distinctly noted from the activation volume of dislocations. The proposed hypothesis was tested by varying the grain size and also the test temperature. Activation volume of dislocations was a strong function of temperature and increased with temperature. And the reduction in grain ...
An Initial Study of Binary and Ternary Ti-based Alloys Manufactured Using Laser Engineered Net Shaping (LENSTM)
In this study an initial assessment of the composition – microstructure – property relationships in binary and ternary Ti – based systems are made possible using LENSTM technology. Laser Engineering Net Shaping (LENSTM), a rapid prototyping, directed laser deposition methodology of additive manufacturing (AM) was used to create bulk homogenous specimens that are compositionally graded. Compositionally graded specimens were made possible by incorporating elemental blends of powder during the LENSTM process. While there have been numerous studies assessing the influence of common elements (e.g., V, Mo, Al, and Cr) on the resulting microstructure in titanium alloys, other elements have been neglected. A systematic study of the Ti – Fe – Al ternary system based upon varying compositions of the eutectoid former, Fe with Al to stabilize the a and b phases respectively has also been neglected. This research effort focuses on exploiting the LENSTM process by rapidly assessing the composition – microstructure – property relationships in a combinatorial approach for the Ti – W, Ti – Fe, and Ti – Fe – Al systems. Compositionally graded specimens of Ti – xW (0<x<40wt.%(14.79at.%)), Ti – xFe (0<x<35wt.%(36.37at.%)), and Ti – xFe – yAl (0<x<40wt.%(36.37at.%)), y=5,10, 15wt.%) have been heat treated to also assess the influence of thermal history on microstructural features such as phase composition and volume fraction. Lastly, a Ti – xMo (0<x<40wt.%(24.96at.%)) compositionally graded specimen was deposited to re-assess the Mo-equivalency nature of W, as well as assess the role of phase separation in microstructural evolution at temperatures above and below the invariant point (~695°C) of the Ti – W binary system.
Characterization of Ti-6Al-4V Produced Via Electron Beam Additive Manufacturing
In recent years, additive manufacturing (AM) has become an increasingly promising method used for the production of structural metallic components. There are a number of reasons why AM methods are attractive, including the ability to produce complex geometries into a near-net shape and the rapid transition from design to production. Ti-6Al-4V is a titanium alloy frequently used in the aerospace industry which is receiving considerable attention as a good candidate for processing via electron beam additive manufacturing (EBAM). The Sciaky EBAM method combines a high-powered electron beam, weld-wire feedstock, and a large build chamber, enabling the production of large structural components. In order to gain wide acceptance of EBAM of Ti-6Al-4V as a viable manufacturing method, it is important to understand broadly the microstructural features that are present in large-scale depositions, including specifically: the morphology, distribution and texture of the phases present. To achieve such an understanding, stereological methods were used to populate a database quantifying key microstructural features in Ti-6Al-4V including volume fraction of phases, a lath width, colony scale factor, and volume fraction of basket weave type microstructure. Microstructural features unique to AM, such as elongated grains and banded structures, were also characterized. Hardness and tensile testing were conducted and the results were related to the microstructural morphology and sample orientation. Lastly, fractured surfaces and defects were investigated. The results of these activities provide insight into the process-structure-properties relationships found in EBAM processed Ti-6Al-4V.
Effect of Alloy Composition, Free Volume and Glass Formability on the Corrosion Behavior of Bulk Metallic Glasses
Bulk metallic glasses (BMGs) have received significant research interest due to their completely amorphous structure which results in unique structural and functional properties. Absence of grain boundaries and secondary phases in BMGs results in high corrosion resistance in many different environments. Understanding and tailoring the corrosion behavior can be significant for various structural applications in bulk form as well as coatings. In this study, the corrosion behavior of several Zr-based and Fe-Co based BMGs was evaluated to understand the effect of chemistry as well as quenched in free volume on corrosion behavior and mechanisms. Presence of Nb in Zr-based alloys was found to significantly improve corrosion resistance due to the formation of a stable passive oxide. Relaxed glasses showed lower rates compared to the as-cast alloys. This was attributed to lowering of chemical potential from the reduced fraction of free volume. Potentiodynamic polarization and Electrochemical Impedance Spectroscopy (EIS) techniques helped in quantifying the corrosion rate and polarization resistance. The effect of alloy composition was quantified by extensive surface analysis using Raman spectroscopy, energy dispersive x-ray spectroscopy and auger spectroscopy. Pitting intensity was higher in the as-cast glasses than the relaxed glasses. The electrochemical behavior of a Zr-Ti-Cu-Ni-Be bulk metallic glass subjected to high strain processing was studied. High strain processing caused shear band formation and an increase in the free volume. Potentiodynamic polarization and EIS showed a strong correlation between the enthalpy of structural relaxation and corrosion rate and polarization resistance. Pitting was observed to preferentially occur on shear bands in the processed samples, while it was stochastic in unprocessed glass. The corrosion analysis of Co-Fe glasses showed an increase in corrosion current density when Fe content was increased from 0 to 7 at%. The corrosion resistance improved when Fe content was further increased to 15 at%. Similar trend was ...
Determining the Emissivity of Roofing Samples: Asphalt, Ceramic and Coated Cedar
The goal is to perform heat measurements examine of selected roofing material samples. Those roofing materials are asphalt shingles, ceramics, and cedar. It’s important to understand the concept of heat transfer, which consists of conduction, convection, and radiation. Research work was reviewed on different infrared devices to see which one would be suitable for conducting my experiment. In this experiment, the main focus was on a specific property of radiation. That property is the emissivity, which is the amount of heat a material is able to radiate compared to a blackbody. An infrared measuring device, such as the infrared camera was used to determine the emissivity of each sample by using a measurement formula consisting of certain equations. These equations account for the emissivity, transmittance of heat through the atmosphere and temperatures of the samples, atmosphere and background. The experiment verifies how reasonable the data is compared to values in the emissivity table. A blackbody method such as electrical black tape was applied to help generate the correct data. With this data obtained, the emissivity was examined to understand what factors and parameters affect this property of the materials. This experiment was conducted using a suitable heat source to heat up the material samples to high temperature. The measurements were taken during the experiment and displayed by the IR camera. The IR images show the behavior of surface temperatures being distributed throughout the different materials. The main challenge was to determine the most accurate emissivity values for all material samples. The results obtained by the IR camera were displayed in figures and tables at different distances, which was between the heap lamp and materials. The materials exhibited different behaviors in temperature and emissivity at certain distances. The emissivity of each material varied with different temperatures. The results led to suggestions ...
Ternary Oxide Structures for High Temperature Lubrication
In this research, a temperature dependent tribological investigation of selected ternary oxides was undertaken. Based on the promising results of previous studies on silver based ternary oxides, copper based ternary oxides were selected to conduct a comparative study since both copper and silver are located in the same group in the periodic table of the elements. Two methods were used to create ternary oxides: (i) solid chemical synthesis to create powders and (ii) sputtering to produce thin films. X-ray diffraction was used to explore the evolution of phases, chemical properties, and structural properties of the coatings before and after tribotesting. Scanning electron microscopy, Auger scanning nanoprobe spectroscopy, and X-ray photoelectron spectroscopy were used to investigate the chemical and morphological properties of these materials after sliding tests. These techniques revealed that chameleon coatings of copper ternary oxides produce a friction coefficient of 0.23 when wear tested at 430 °C. The low friction is due to the formation of copper tantalate phase and copper in the coatings. All sputtering coatings showed similar tribological properties up to 430 °C.
First Principles Study of Metastable Beta Titanium Alloys
The high temperature BCC phase (b) of titanium undergoes a martensitic transformation to HCP phase (a) upon cooling, but can be stabilized at room temperature by alloying with BCC transition metals such as Mo. There exists a metastable composition range within which the alloyed b phase separates into a + b upon equilibrium cooling but not when rapidly quenched. Compositional partitioning of the stabilizing element in as-quenched b microstructure creates nanoscale precipitates of a new simple hexagonal w phase, which considerably reduces ductility. These phase transformation reactions have been extensively studied experimentally, yet several significant questions remain: (i) The mechanism by which the alloying element stabilizes the b phase, thwarts its transformation to w, and how these processes vary as a function of the concentration of the stabilizing element is unclear. (ii) What is the atomistic mechanism responsible for the non-Arrhenius, anomalous diffusion widely observed in experiments, and how does it extend to low temperatures? How does the concentration of the stabilizing elements alter this behavior? There are many other w forming alloys that such exhibit anomalous diffusion behavior. (iii) A lack of clarity remains on whether w can transform to a -phase in the crystal bulk or if it occurs only at high-energy regions such as grain boundaries. Furthermore, what is the nature of the a phase embryo? (iv) Although previous computational results discovered a new wa transformation mechanism in pure Ti with activation energy lower than the classical Silcock pathway, it is at odds with the a / b / w orientation relationship seen in experiments. First principles calculations based on density functional theory provide an accurate approach to study such nanoscale behavior with full atomistic resolution, allowing investigation of the complex structural and chemical effects inherent in the alloyed state. In the present work, a model Ti-Mo ...
Precession Electron Diffraction Assisted Characterization of Deformation in α and α+β Titanium Alloys
Ultra-fine grained materials with sub-micrometer grain size exhibit superior mechanical properties when compared with conventional fine-grained material as well as coarse-grained materials. Severe plastic deformation (SPD) techniques have been shown to be an effective way to modify the microstructure in order to improve the mechanical properties of the material. Crystalline materials require dislocations to accommodate plastic strain gradients and maintain lattice continuity. The lattice curvature exists due to the net dislocation that left behind in material during deformation. The characterization of such defects is important to understand deformation accumulation and the resulting mechanical properties of such materials. However, traditional techniques are limited. For example, the spatial resolution of EBSD is insufficient to study materials processed via SPD, while high dislocation densities make interpretations difficult using conventional diffraction contrast techniques in the TEM. A new technique, precession electron diffraction (PED) has gained recognition in the TEM community to solve the local crystallography, including both phase and orientation, of nanocrystalline structures under quasi-kinematical conditions. With the assistant of precession electron diffraction coupled ASTARÔ, the structure evolution of equal channel angular pressing processed commercial pure titanium is studied; this technique is also extended to two-phase titanium alloy (Ti-5553) to investigate the existence of anisotropic deformation behavior of the constituent alpha and beta phases.
Combinatorial Assessment of the Influence of Composition and Exposure Time on the Oxidation Behavior and Concurrent Oxygen-induced Phase Transformations of Binary Ti-x Systems
The relatively low oxidation resistance and subsequent surface embrittlement have often limited the use of titanium alloys in elevated temperature structural applications. Although extensive effort is spent to investigate the high temperature oxidation performance of titanium alloys, the studies are often constrained to complex technical titanium alloys and neither the mechanisms associated with evolution of the oxide scale nor the effect of oxygen ingress on the microstructure of the base metal are well-understood. In addition lack of systematic oxidation studies across a wider domain of the alloy composition has complicated the determination of composition-mechanism-property relationships. Clearly, it would be ideal to assess the influence of composition and exposure time on the oxidation resistance, independent of experimental variabilities regarding time, temperature and atmosphere as the potential source of error. Such studies might also provide a series of metrics (e.g., hardness, scale, etc) that could be interpreted together and related to the alloy composition. In this thesis a novel combinatorial approach was adopted whereby a series of compositionally graded specimens, (Ti-xMo, Ti-xCr, Ti-xAl and Ti-xW) were prepared using Laser Engineered Net Shaping (LENS™) technology and exposed to still-air at 650 °C. A suite of the state-of-the-art characterization techniques were employed to assess several aspects of the oxidation reaction as a function of local average composition including: the operating oxidation mechanisms; the structure and composition of the oxides; the oxide adherence and porosity; the thickness of the oxide layers; the depth of oxygen ingress; and microstructural evolution of the base material just below the surface but within the oxygen-enriched region. The results showed that for the Ti-Mo, Ti-Al and Ti-W systems a parabolic oxidation rate law is obeyed in the studied composition-time domain while Ti-Cr system experiences a rapid breakaway oxidation regime at low solute concentrations. The only titanium oxide phase present in ...
Atomistic Simulations of Deformation Mechanisms in Ultra-Light Weight Mg-Li Alloys
Mg alloys have spurred a renewed academic and industrial interest because of their ultra-light-weight and high specific strength properties. Hexagonal close packed Mg has low deformability and a high plastic anisotropy between basal and non-basal slip systems at room temperature. Alloying with Li and other elements is believed to counter this deficiency by activating non-basal slip by reducing their nucleation stress. In this work I study how Li addition affects deformation mechanisms in Mg using atomistic simulations. In the first part, I create a reliable and transferable concentration dependent embedded atom method (CD-EAM) potential for my molecular dynamics study of deformation. This potential describes the Mg-Li phase diagram, which accurately describes the phase stability as a function of Li concentration and temperature. Also, it reproduces the heat of mixing, lattice parameters, and bulk moduli of the alloy as a function of Li concentration. Most importantly, our CD-EAM potential reproduces the variation of stacking fault energy for basal, prismatic, and pyramidal slip systems that influences the deformation mechanisms as a function of Li concentration. This success of CD-EAM Mg-Li potential in reproducing different properties, as compared to literature data, shows its reliability and transferability. Next, I use this newly created potential to study the effect of Li addition on deformation mechanisms in Mg-Li nanocrystalline (NC) alloys. Mg-Li NC alloys show basal slip, pyramidal type-I slip, tension twinning, and two-compression twinning deformation modes. Li addition reduces the plastic anisotropy between basal and non-basal slip systems by modifying the energetics of Mg-Li alloys. This causes the solid solution softening. The inverse relationship between strength and ductility therefore suggests a concomitant increase in alloy ductility. A comparison of the NC results with single crystal deformation results helps to understand the qualitative and quantitative effect of Li addition in Mg on nucleation stress and fault ...
Plasma Interactions on Organosilicate Glass Dielectric Films and Emerging Amorphous Materials- Approach to Pore Sealing and Chemical Modifications
In-situ x-ray photoemission (XPS) and ex-situ FTIR studies of nanoporous organosilicate glass (OSG) films point to the separate roles of radicals vs. VUV photons in the carbon abstraction. The studies indicate that reaction with O2 in presence of VUV photons (~123 nm) result in significant carbon abstraction within the bulk and that the kinetics of this process is diffusion-limited. In contrast, OSG exposed to atomic O (no VUV) results in Si-C bond scission and Si-O bond formation, but this process is self-limiting after formation of ~1 nm thick SiO2 surface layer that inhibits further diffusion. Therefore, the diffusion-dominated kinetics of carbon abstraction observed for OSG exposed to O2 plasma is definitively attributed to the diffusion of O2 down OSG nanopores, reacting at photo-activated sites, rather than to the diffusion of atomic O. Pretreatment of OSG by 900 eV Ar+ ion bombardment also results in formation of 1 nm thick SiO2-like surface overlayer that inhibits O2 diffusion, inhibiting VUV+O2 and O2 plasma-induced reactions, and that the effectiveness of this treatment increases with ion kinetic energy. On the contrary, organosilicate glass (OSG) films with backbone carbon (-Si-R-Si-) exhibit significantly enhanced resistance to carbon loss upon exposure to O2 plasma, radicals and VUV+O2 compared to films with terminal methyl groups (Si-CH3). Films incorporating backbone carbon chains (-Si-R-Si-) were deposited from 1,2 bis (triethoxysilyl) ethane (BTESE) precursor by ebeam or plasma cross-linking. The radical effects on BTESE film indicates negligible carbon loss or Si oxidation, combined with C-O bond formation, under conditions where OSG films with terminal methyl groups exhibit > 80% carbon loss within the surface region of the film. C-O bond formation is never observed for terminal CH3 groups. Further, backbone carbon (-Si-R-Si-) films exposed to VUV+O2 exhibit self-limiting, minimal net carbon loss. This indicates that plasma-induced Si-C bond rupture still occurs ...
Surface Topography and Aesthetics of Recycled Cross-Linked Polyethylene Wire and Cable Coatings
Our research focuses on re-using a waste a material, cross-linked polyethylene abbreviated XLPE, which is a widely used coating for wires. XLPE is strong and has excellent thermal properties due to its chemical structure - what leads to the significance of recycling this valuable polymer. Properties of XLPE include good resistance to heat, resistance to chemical corrosion, and high impact strength. A wire is usually composed of a metal core conductor and polymeric coating layers. One creates a new coating, including little pieces of recycled XLPE in the lower layer adjacent to the wire, and virgin XLPE only in the upper layer. Industries are often wasting materials which might be useful. Mostly, some returned or excess products could be recycled to create a new type of product or enable the original use. This method helps cleaning the waste, lowers the costs, and enhances the income of the manufacturing company. With the changing of the thickness of the outer layer, the roughness changes significantly. Moreover, different processing methods result in surfaces that look differently.
Nanohybrids Based on Solid and Foam Polyurethanes
Polymer nanocomposites are a going part of Materials Science and Engineering. These new composite materials exhibit dimensional and thermal stability of inorganic materials and toughness and dielectric properties of polymers. Development of nanocomposites become an important approach to create high-performance composite materials. In this study silica, fly ash, silica nanotubes and carbon black particles have been added to modify polyurethane foam and thermoplastic polyurethanes. It has been found that the addition of silica can diminish the size of foam bubbles, resulting in an increased stiffness of the material, increase of the compressive strength, and greater resistance to deformation. However, the uniformity of bubbles is reduced, resulting in increased friction of the material. Fly ash added to the foam can make bubbles smaller and improve uniformity of cells. Therefore, the material stiffness and compressive strength, resistance to deformation, and has little impact on the dynamic friction of the material. Adding nanotubes make bubble size unequal, and the arrangement of the bubble uneven, resulting in decreased strength of the material, while the friction increases. After the addition of carbon black to the polyurethane foam, due to the special surface structure of the carbon black, the foam generates more bubbles during the foaming process changing the foam structure. Therefore, the material becomes soft, we obtain a flexible polyurethane foam. The results of mechanical properties determination of the thermoplastic polyurethane that adding particles may increase the stiffness and wear resistance of the thermoplastic polyurethane, while the tensile properties of the material are reduced. This phenomenon may be due to agglomeration of particles during the mixing process. Possibly the particles cannot be uniformly dispersed in the thermoplastic polyurethane.
An Assessment of Uncommon Titanium Binary Systems: Ti-Zn, Ti-Cu, and Ti-Sb
The current study focuses on phase stability and evolution in the titanium-zinc titanium-copper and titanium-antimony systems. The study utilized the Laser Engineering Net Shaping (LENS™) processing technique to deposit compositionally graded samples of three binary system in order to allow the assessment of phase stability and evolution as a function of composition and temperature the material is subjected to. Through LENS™ processing it was possible to create graded samples from Ti-xSb (up to 13wt%) and Ti-xCu (up to 16wt%). The LENS™ deposited gradient were solutionized, and step quenched to specific aging temperature, and the resulting microstructures and phase were characterized utilizing XRD, EDS, SEM, FIB and TEM. The Ti-Zn system proved incapable of being LENS™ deposited due to the low vaporization temperature of Zn; however, a novel processing approach was developed to drip liquid Zn onto Ti powder at temperatures above β transus temperature of Ti (882 ◦C) and below the vaporization temperature of Zn (907 ◦C). The product of this processing technique was characterized in a similar way as the graded LENS™ depositions. From measurements performed on Ti-Sb it seems that Sb could be a potential α stabilizer in Ti due to the presence of a mostly homogeneous α grains throughout the gradient; however, from XRD it can be understood that a titanium antimonide phase is present. From results obtained from the Ti-Zn samples, it can be surmised that the eutectoid reaction seems to be active, i.e. The eutectoid reaction is kinetically fast, as concluded by the presence of pearlitic structures. Finally, for the Ti-Cu system this work has been attempted to prove or disprove the existence of the Ti3Cu through the use of XRD and TEM SAD patterns. From XRD spectra collected there are peaks belonging to the Ti3Cu orthorhombic phase along with Ti2Cu and α-Ti phase. In ...
Processing and Characterization of Polycarbonate Foams with Supercritical Co2 and 5-Phenyl-1H-tetrazole
Since their discovery in the 1930s, polymeric foams have been widely used in the industry for a variety of applications such as acoustical and thermal insulation, filters, absorbents etc. The reason for this ascending trend can be attributed to factors such as cost, ease of processing and a high strength to weight ratio compared to non-foamed polymers. The purpose of this project was to develop an “indestructible” material made of polycarbonate (PC) for industrial applications. Due to the high price of polycarbonate, two foaming methods were investigated to reduce the amount of material used. Samples were foamed physically in supercritical CO2 or chemically with 5-phenyl-1H-tetrazole. After thermal characterization of the foams in differential scanning calorimetry (DSC), we saw that none of the foaming methods had an influence on the glass transition of polycarbonate. Micrographs taken in scanning electron microscopy (SEM) showed that foams obtained in physical and chemical foaming had different structures. Indeed, samples foamed in supercritical CO2 exhibited a microcellular opened-cell structure with a high cell density and a homogeneous cell distribution. On the other hand, samples foamed with 5-phenyl-1H-tetrazole had a macrocellular closed-cell structure with a much smaller cell density and a random cell distribution. Compression testing showed that polycarbonate foamed physically had a compression modulus a lot greater. Then, XLPE mesh 35 or 50 and wollastonite were added to the polymeric matrices to enhance the foaming process and the mechanical properties. DSC experiments showed that the addition of fillers changed the thermal properties of polycarbonate for both foaming methods by inducing a shift in glass transition. SEM revealed that fillers lowered the average cell diameter and increased the cell density. This phenomenon increased the compression modulus for polycarbonate foamed in supercritical CO2. However, mechanical properties decreased for samples foamed with 5-phenyl-1H-tetrazole due to their relative brittleness and ...
Processing, Structure and Tribological Property Relations of Ternary Zn-Ti-O and Quaternary Zn-Ti-Zr-O Nanocrystalline Coatings
Conventional liquid lubricants are faced with limitations under extreme cyclic operating conditions, such as in applications that require lubrication when changing from atmospheric pressure to ultrahigh vacuum and ambient air to dry nitrogen (e.g., satellite components), and room to elevated (>500°C) temperatures (e.g., aerospace bearings). Alternatively, solid lubricant coatings can be used in conditions where synthetic liquid lubricants and greases are not applicable; however, individual solid lubricant phases usually perform best only for a limited range of operating conditions. Therefore, solid lubricants that can adequately perform over a wider range of environmental conditions are needed, especially during thermal cycling with temperatures exceeding 500°C. One potential material class investigated in this dissertation is lubricious oxides, because unlike other solid lubricant coatings they are typically thermodynamically stable in air and at elevated temperatures. While past studies have been focused on binary metal oxide coatings, such as ZnO, there have been very few ternary oxide and no reported quaternary oxide investigations. The premise behind the addition of the third and fourth refractory metals Ti and Zr is to increase the number of hard and wear resistant phases while maintaining solid lubrication with ZnO. Therefore, the major focus of this dissertation is to investigate the processing-structure-tribological property relations of composite ZnO, TiO2 and ZrO2 phases that form ternary (ZnTi)xOy and quaternary (ZnTiZr)xOy nanocrystalline coatings. The coatings were processed by atomic layer deposition (ALD) using a selective variation of ALD parameters. The growth structure and chemical composition of as-deposited and ex situ annealed ternary and quaternary oxide coatings were studied by combined x-ray diffraction/focused ion beam microscopy/cross-sectional transmission electron microscopy, and x-ray photoelectron spectroscopy/Auger electron spectroscopy, respectively. It was determined that the structure varied from purely nanocrystalline (ternary oxides) to composite amorphous/nanocrystalline (quaternary oxides) depending on ALD parameters and annealing temperatures. In particular, the ZnTiO3 ...
Structural, Thermal and Acoustic Performance of Polyurethane Foams for Green Buildings
Decreasing the carbon footprint through use of renewable materials has environmental and societal impact. Foams are a valuable constituent in buildings by themselves or as a core in sandwich composites. Kenaf is a Southeast USA plant that provides renewable filler. The core of the kenaf is porous with a cell size in a 5-10 micrometer range. The use of kenaf core in foams represents a novel multiscalar cellular structural composite. Rigid polyurethane foams were made using free foaming expansion with kenaf core as filler with loadings of 5, 10 and 15 %. Free foaming was found to negatively affect the mechanical properties. An innovative process was developed to introduce a constraint to expansion during foaming. Two expansion ratios were examined: 40 and 60 % (decreasing expansion ratio). MicroCT and SEM analysis showed a varying structure of open and closed cell pores. The mechanical, thermal insulation, acoustic properties were measured. Pure PU foam showed improved cell size uniformity. Introducing kenaf core resulted in decreasing the PU performance in the free expansion case. This was reversed by introducing constraints. To understand the combined impact of having a mixed close cell and open cell architecture, finite element modeling was done using ANSYS. Models were created with varying percentages of open, closed, and bulk cells to encompass entire range of foam porosities. Net zero energy building information modelling was conducted using EnergyPlus was conducted using natural fiber composite skins. Environmental impacts for instance global warming potential, acidification, eutrophication, fossil fuel consumption, ozone depletion, and smog potential of the materials used in construction was studied using life cycle assessment. The results showed improvement on energy consumption and carbon footprint.
Growth Mechanisms, and Mechanical and Thermal Properties of Junctions in 3D Carbon Nanotube-Graphene Nano-Architectures
Junctions are the key component for 3D carbon nanotube (CNT)-graphene seamless hybrid nanostructures. Growth mechanism of junctions of vertical CNTs growing from graphene in the presence of iron catalysts was simulated via quantum mechanical molecular dynamics (QM/MD) methods. CNTs growth from graphene with iron catalysts is based on a ‘‘base-growth’’ mechanism, and the junctions were the mixture of C-C and Fe-C covalent bonds. Pure C-C bonded junctions could be obtained by moving the catalyst during CNT growth or etching and annealing after growth. The growth process of 3D CNT-graphene junctions on copper templates with nanoholes was simulated with molecular dynamic (MD) simulation. There are two mechanisms of junction formation: (i) CNT growth over the holes that are smaller than 3 nm, and (ii) CNT growth inside the holes that are larger than 3 nm. The growth process of multi-layer filleted CNT-graphene junctions on the Al2O3 template was also simulated with MD simulation. A simple analytical model is developed to explain that the fillet takes the particular angle (135°). MD calculations show that 135° filleted junction has the largest fracture strength and thermal conductivity at room temperature compared to junctions with 90°,120°, 150°, and 180° fillets. The tensile strengths of the as-grown C–C junctions, as well as the junctions embedded with metal nanoparticles (catalysts), were determined by a QM/MD method. Metal catalysts remaining in the junctions significantly reduce the fracture strength and fracture energy. Moreover, the thermal conductivities of the junctions were also calculated by MD method. Metal catalysts remaining in the junctions considerably lower the thermal conductivity of the 3D junctions.
Atomistic Computer Simulations of Diffusion Mechanisms in Lithium Lanthanum Titanate Solid State Electrolytes for Lithium Ion Batteries
Solid state lithium ion electrolytes are important to the development of next generation safer and high power density lithium ion batteries. Perovskite-structured LLT is a promising solid electrolyte with high lithium ion conductivity. LLT also serves as a good model system to understand lithium ion diffusion behaviors in solids. In this thesis, molecular dynamics and related atomistic computer simulations were used to study the diffusion behavior and diffusion mechanism in bulk crystal and grain boundary in lithium lanthanum titanate (LLT) solid state electrolytes. The effects of defect concentration on the structure and lithium ion diffusion behaviors in LLT were systematically studied and the lithium ion self-diffusion and diffusion energy barrier were investigated by both dynamic simulations and static calculations using the nudged elastic band (NEB) method. The simulation results show that there exist an optimal vacancy concentration at around x=0.067 at which lithium ions have the highest diffusion coefficient and the lowest diffusion energy barrier. The lowest energy barrier from dynamics simulations was found to be around 0.22 eV, which compared favorably with 0.19 eV from static NEB calculations. It was also found that lithium ions diffuse through bottleneck structures made of oxygen ions, which expand in dimension by 8-10% when lithium ions pass through. By designing perovskite structures with large bottleneck sizes can lead to materials with higher lithium ion conductivities. The structure and diffusion behavior of lithium silicate glasses and their interfaces, due to their importance as a grain boundary phase, with LLT crystals were also investigated by using molecular dynamics simulations. The short and medium range structures of the lithium silicate glasses were characterized and the ceramic/glass interface models were obtained using MD simulations. Lithium ion diffusion behaviors in the glass and across the glass/ceramic interfaces were investigated. It was found that there existed a minor segregation ...
Computational Studies on Structures and Ionic Diffusion of Bioactive Glasses
Bioactive glasses are a class of synthetic inorganic material that have wide orthopedics, dentistry, tissue engineering and other biomedical applications. The origin of the bioactivity is closely related to the atomic structures of these novel glass materials, which otherwise lack long range order and defies any direct experimental measurements due to their amorphous nature. The structure of bioactive glasses is thus essential for the understanding of bioactive behaviors and eventually rational design of glass compositions. In this dissertation, molecular dynamics (MD) and reverse monte carlo (RMC) based computer simulations have been used to systematically study the atomic structure of three classes of new bioactive glasses: strontium doped 45S5 Bioglass®, ZnO-SrO containing bioactive glasses, and Cao-MgO-P2O5-SiO2 bioactive glasses. Properties such as ionic diffusion that are important to glass dissolution behaviors are also examined as a function of glass compositions. The accuracy of structure model generated by simulation was validated by comparing with various experimental measurements including X-ray/neutron diffraction, NMR and Raman spectroscopy. It is shown in this dissertation that atomistic computer simulations, when integrated with structural and property characterizations, is an effective tool in understanding the structural origin of bioactivity and other properties of amorphous bioactive materials that can lead to design of novel materials for biomedical applications.
Computational Study of Dislocation Based Mechanisms in FCC Materials
Understanding the relationships between microstructures and properties of materials is a key to developing new materials with more suitable qualities or employing the appropriate materials in special uses. In the present world of material research, the main focus is on microstructural control to cost-effectively enhance properties and meet performance specifications. This present work is directed towards improving the fundamental understanding of the microscale deformation mechanisms and mechanical behavior of metallic alloys, particularly focusing on face centered cubic (FCC) structured metals through a unique computational methodology called three-dimensional dislocation dynamics (3D-DD). In these simulations, the equations of motion for dislocations are mathematically solved to determine the evolution and interaction of dislocations. Microstructure details and stress-strain curves are a direct observation in the simulation and can be used to validate experimental results. The effect of initial dislocation microstructure on the yield strength has been studied. It has been shown that dislocation density based crystal plasticity formulations only work when dislocation densities/numbers are sufficiently large so that a statistically accurate description of the microstructure can be obtainable. The evolution of the flow stress for grain sizes ranging from 0.5 to 10 µm under uniaxial tension was simulated using an improvised model by integrating dislocation pile-up mechanism at grain boundaries has been performed. This study showed that for a same initial dislocation density, the Hall–Petch relationship holds well at small grain sizes (0.5–2 µm), beyond which the yield strength remains constant as the grain size increases.
Gamma Prime Precipitation Mechanisms and Solute Partitioning in Ni-base Alloys
Nickel-base superalloys have been emerged as materials for gas turbines used for jet propulsion and electricity generation. The strength of the superalloys depends mainly from an ordered precipitates of L12 structure, so called gamma prime (γ’) dispersed within the disorder γ matrix. The Ni-base alloys investigated in this dissertation comprise both model alloy systems based on Ni-Al-Cr and Ni-Al-Co as well as the commercial alloy Rene N5. Classical nucleation and growth mechanism dominates the γ’ precipitation process in slowed-cooled Ni-Al-Cr alloys. The effect of Al and Cr additions on γ’ precipitate size distribution as well as morphological and compositional development of γ’ precipitates were characterized by coupling transmission electron microscopy (TEM) and 3D atom probe (3DAP) techniques. Rapid quenching Ni-Al-Cr alloy experiences a non-classical precipitation mechanism. Structural evolution of the γ’ precipitates formed and subsequent isothermal annealing at 600 °C were investigated by coupling TEM and synchrotron-based high-energy x-ray diffraction (XRD). Compositional evolution of the non-classically formed γ’ precipitates was determined by 3DAP and Langer, Bar-on and Miller (LBM) method. Besides homogeneous nucleation, the mechanism of heterogeneous γ’ precipitation involving a discontinuous precipitation mechanism, as a function of temperature, was the primary focus of study in case of the Ni-Al-Co alloy. This investigation coupled SEM, SEM-EBSD, TEM and 3DAP techniques. Lastly, solute partitioning and enrichment of minor refractory elements across/at the γ/ γ’ interfaces in the commercially used single crystal Rene N5 superalloy was investigated by using an advantage of nano-scale composition investigation of 3DAP technique.
Laser Surface Alloying of Refractory Metals on Aluminum for Enhanced Corrosion Resistance: Experimental and Computational Approaches
Aluminum (Al) and its alloys are widely used in various technological applications, mainly due to the excellent thermal conductivity, non-magnetic, ecofriendly, easy formability and good recyclability. However due to the inferior corrosion resistance its applications are hampered in various engineering sectors. Besides, the corrosion related failures such as leakage of gas from pipeline, catastrophic breakdown of bridges and fire accidents in processing plants further puts the human life in jeopardy. Within the United States over $ 400 billion dollars per year are spent over research to understand and prevent the corrosion related failures. Recently, the development of transition metal(TM) aluminides (AlxTMy, where, TM = Mo, W, Ta, Nb, Cr, Zr and V) has received the global attention mainly due to high strength at elevated temperatures, light-weight, excellent corrosion and wear resistance. In light of this, surface modification via laser surface alloying (LSA) is a promising engineering approach to mitigate the corrosion and wear problems. In the present study the attempts are made to study the Al-Mo, Al-W, Al-Nb, and Al-Ta systems as a potential corrosion resistant coatings on aluminum. The refractory metal (Mo, W, Nb, Ta) precursor deposit was spray coated separately on aluminum substrate and was subsequently surface alloyed using a continuous wave diode-pumped ytterbium laser at varying laser energy densities. Microstructural analysis was conducted using scanning electron microscopy and further X-ray diffractometry was carried out to evaluate the various phases evolved during laser surface alloying. Corrosion resistance of laser alloyed coatings were evaluated using open circuit potential, cyclic potentiodynamic polarization, electrochemical impedance spectroscopy measurements were performed in 0.6 M NaCl solution (pH:6.9±0.2, 23˚C). Open circuit potential measurements indicate the more stable (steady state) potential values over long periods after laser surface alloying. Cyclic polarization results indicated reduction in the corrosion current density, enhancement in the polarization resistance, and ...
Silver Tantalate: a High Temperature Tribological Investigation
As technology advances, mechanical and electrical systems are subjugated to intense temperature fluctuations through their service life. Designing coatings that operate in extreme temperatures is, therefore, a continuing challenge within the tribology community. Silver tantalate was chosen for investigation at the atomic level, the physical and chemical properties that influence the thermal, mechanical, and tribological behavior for moving assemblies in high temperature tribological applications. By correlating behavior of internal physical processes to the macro tribological behavior, the tribological community will potentially gain improved predicative performance of solid lubricants in future investigations. Three different approaches were explored for the creation of such materials on Inconel substrates: (1) powders produced using a solid state which were burnished on the surface; (2) monolithic silver tantalate thin films deposited by magnetron sputtering; and, (3) an adaptive tantalum nitride/silver nanocomposite sputter-deposited coating that forms a lubricious silver tantalate oxide on its surface when operated at elevated temperatures. Dry sliding wear tests of the coatings against Si3N4 counterfaces revealed friction coefficients in the 0.06 - 0.15 range at T ~ 750 °C. Reduced friction coefficients were found in nanocomposite materials that contained primarily a AgTaO3 phase with a small amount of segregated Ag phase, as suggested by structural characterization using X-ray diffraction. The presence of nanoparticles of segregated Ag in the thin films further enhanced the performance of these materials by increasing their toughness. Additional characterization of the AgTaO3 films at 750 °C under normal loads of 1, 2, 5, or 10 N revealed that the friction monotonically increased as the load was increased. These results were complemented by molecular dynamics simulations, which confirmed the increase of friction with load. Further, the simulations support the hypothesis that this trend can be explained in terms of decreased presence of Ag clusters near the sliding surface and the ...
A Study of Power Generation From a Low-cost Hydrokinetic Energy System
The kinetic energy in river streams, tidal currents, or other artificial water channels has been used as a feasible source of renewable power through different conversion systems. Thus, hydrokinetic energy conversion systems are attracting worldwide interest as another form of distributed alternative energy. Because these systems are still in early stages of development, the basic approaches need significant research. The main challenges are not only to have efficient systems, but also to convert energy more economically so that the cost-benefit analysis drives the growth of this alternative energy form. One way to view this analysis is in terms of the energy conversion efficiency per unit cost. This study presents a detailed assessment of a prototype hydrokinetic energy system along with power output costs. This experimental study was performed using commercial low-cost blades of 20 in diameter inside a tank with water flow speed up to 1.3 m/s. The work was divided into two stages: (a) a fixed-pitch blade configuration, using a radial permanent magnet generator (PMG), and (b) the same hydrokinetic turbine, with a variable-pitch blade and an axial-flux PMG. The results indicate that even though the efficiency of a simple blade configuration is not high, the power coefficient is in the range of other, more complicated designs/prototypes. Additionally, the low manufacturing and operation costs of this system offer an option for low-cost distributed power applications.
Surface Modifications to Enhance the Wear Resistance and the Osseo-integration Properties of Biomedical Ti-alloy
The current study focuses on improving the wear resistance of femoral head component and enhancing the osseo-integration properties of femoral stem component of a hip implant made of a new generation low modulus alloy, Ti-35Nb-7Zr-5Ta or TNZT. Different techniques that were adopted to improve the wear resistance of low-modulus TNZT alloy included; (a) fabrication of graded TNZT-xB (x= 0, 1, 2 wt%) samples using LENS, (b) oxidation, and (c) LASER nitriding of TNZT. TNZT-1B and TNZT-O samples have shown improved wear resistance when tested against UHMWPE ball in SBF medium. A new class of bio-ceramic coatings based on calcium phosphate (CaP), was applied on the TNZT sample surface and was further laser processed with the objective of enhancing their osseo-integration properties. With optimized LASER parameters, TNZT-CaP samples have shown improved corrosion resistance, surface wettability and cellular response when compared to the base TNZT sample.
Thermoplastic and Thermoset Natural Fiber Composite and Sandwich Performance
The objective of this thesis is to investigate the effects of adding natural fiber (kenaf fiber, retted kenaf fiber, and sugarcane fiber) into polymer materials. The effects are obtained by considering three main parts. 1. Performance in thermoplastic composites. The effect of fiber retting on polymer composite crystallization and mechanical performance was investigated. PHBV/PBAT in 80/20 blend ratio was modified using 5% by weight kenaf fiber. Dynamic mechanical analysis of the composites was done to investigate the glass transition and the modulus at sub-ambient and ambient temperatures. ESEM was conducted to analyze fiber topography which revealed smoother surfaces on the pectinase retted fibers. 2. Performance in thermoset composites. The effect of the incorporation of natural fibers of kenaf and of sugarcane combined with the polyester resin matrix is investigated. A comparison of mechanical properties of kenaf polyester composite, sugarcane polyester composite and pure polyester in tensile, bending, dynamic mechanical thermal analysis (DMA) and moisture test on performance is measured.. 3. Performance in sandwich composites. The comparison of the performance characteristics and mechanical properties of natural fiber composites panels with soft and rigid foam cores are evaluated. A thorough test of the mechanical behavior of composites sandwich materials in tensile, bending and DCB is presented here.
Dislocation Dynamics Simulations of Plasticity in Cu Thin Films
Strong size effects in plastic deformation of thin films have been experimentally observed, indicating non-traditional deformation mechanisms. These observations require improved understanding of the behavior of dislocation in small size materials, as they are the primary plastic deformation carrier. Dislocation dynamics (DD) is a computational method that is capable of directly simulating the motion and interaction of dislocations in crystalline materials. This provides a convenient approach to study micro plasticity in thin films. While two-dimensional dislocation dynamics simulation in thin film proved that the size effect fits Hall-Petch equation very well, there are issues related to three-dimensional size effects. In this work, three-dimensional dislocation dynamics simulations are used to study model cooper thin film deformation. Grain boundary is modeled as impenetrable obstacle to dislocation motion in this work. Both tension and cyclic loadings are applied and a wide range of size and geometry of thin films are studied. The results not only compare well with experimentally observed size effects on thin film strength, but also provide many details on dislocation processes in thin films, which could greatly help formulate new mechanisms of dislocation-based plasticity.
Laser Deposition, Heat-treatment, and Characterization of the Binary Ti-xmn System
The present research seeks to characterization of an additively manufactured and heat-treated Ti-xMn gradient alloy, a binary system that has largely been unexplored. In order to rapidly assess this binary system, compositionally graded Ti-xMn (0<x<15 wt%) specimens were fabricated using the LENS (Laser Engineered Net Shaping) and were subsequently heat-treated and characterized using a wide range of techniques. Microstructural changes with respect to the change in thermal treatments, hardness and chemical composition were observed and will be presented. These include assessments of both continuous cooling, leading to observations of both equilibrium and metastable phases, including the titanium martensites, and to direct aging studies looking for composition regimes that produce highly refined alpha precipitates – a subject of great interest given recent understandings of non-classical nucleation and growth mechanisms. The samples were characterized using SEM, EDS, TEM, and XRD and the properties probed using a Vickers Microhardness tester.
Processing and Characterization of Nickel-Carbon Base Metal Matrix Composites
Carbon nanotubes (CNTs) and graphene nanoplatelets (GNPs) are attractive reinforcements for lightweight and high strength metal matrix composites due to their excellent mechanical and physical properties. The present work is an attempt towards investigating the effect of CNT and GNP reinforcements on the mechanical properties of nickel matrix composites. The CNT/Ni (dry milled) nanocomposites exhibiting a tensile yield strength of 350 MPa (about two times that of SPS processed monolithic nickel ~ 160 MPa) and an elongation to failure ~ 30%. In contrast, CNT/Ni (molecular level mixed) exhibited substantially higher tensile yield strength (~ 690 MPa) but limited ductility with an elongation to failure ~ 8%. The Ni-1vol%GNP (dry milled) nanocomposite exhibited the best balance of properties in terms of strength and ductility. The enhancement in the tensile strength (i.e. 370 MPa) and substantial ductility (~40%) of Ni-1vol%GNP nanocomposites was achieved due to the combined effects of grain refinement, homogeneous dispersion of GNPs in the nickel matrix, and well-bonded Ni-GNP interface, which effectively transfers stress across metal-GNP interface during tensile deformation. A second emphasis of this work was on the detailed 3D microstructural characterization of a new class of Ni-Ti-C based metal matrix composites, developed using the laser engineered net shaping (LENSTM) process. These composites consist of an in situ formed and homogeneously distributed titanium carbide (TiC) as well as graphite phase reinforcing the nickel matrix. 3D microstructure helps in determining true morphology and spatial distribution of TiC and graphite phase as well as the phase evolution sequence. These Ni-TiC-C composites exhibit excellent tribological properties (low COF), while maintaining a relatively high hardness.