UNT Theses and Dissertations - 65 Matching Results

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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 ...
Barrier and Long Term Creep Properties of Polymer Nanocomposites.
The barrier properties and long term strength retention of polymers are of significant importance in a number of applications. Enhanced lifetime food packaging, substrates for OLED based flexible displays and long duration scientific balloons are among them. Higher material requirements in these applications drive the need for an accurate measurement system. Therefore, a new system was engineered with enhanced sensitivity and accuracy. Permeability of polymers is affected by permeant solubility and diffusion. One effort to decrease diffusion rates is via increasing the transport path length. We explore this through dispersion of layered silicates into polymers. Layered silicates with effective aspect ratio of 1000:1 have shown promise in improving the barrier and mechanical properties of polymers. The surface of these inorganic silicates was modified with surfactants to improve the interaction with organic polymers. The micro and nanoscale dispersion of the layered silicates was probed using optical and transmission microscopy as well as x-ray diffraction. Thermal transitions were analyzed using differential scanning calorimetry. Mechanical and permeability measurements were correlated to the dispersion and increased density. The essential structure-property relationships were established by comparing semicrystalline and amorphous polymers. Semicrystalline polymers selected were nylon-6 and polyethylene terephthalate. The amorphous polymer was polyethylene terphthalate-glycol. Densification due to the layered silicate in both semicrystalline and amorphous polymers was associated with significant impact on barrier and long term creep behavior. The inferences were confirmed by investigating a semi-crystalline polymer - polyethylene - above and below the glass transition. The results show that the layered silicate influences the amorphous segments in polymers and barrier properties are affected by synergistic influences of densification and uniform dispersion of the layered silicates.
Biocompatible Hybrid Nanomaterials Involving Polymers and Hydrogels Interfaced with Phosphorescent Complexes and Toxin-Free Metallic Nanoparticles for Biomedical Applications
The major topics discussed are all relevant to interfacing brightly phosphorescent and non-luminescent coinage metal complexes of [Ag(I) and Au(I)] with biopolymers and thermoresponsive gels for making hybrid nanomaterials with an explanation on syntheses, characterization and their significance in biomedical fields. Experimental results and ongoing work on determining outreaching consequences of these hybrid nanomaterials for various biomedical applications like cancer therapy, bio-imaging and antibacterial abilities are described. In vitro and in vivo studies have been performed on majority of the discussed hybrid nanomaterials and determined that the cytotoxicity or antibacterial activity are comparatively superior when compared to analogues in literature. Consequential differences are noticed in photoluminescence enhancement from hybrid phosphorescent hydrogels, phosphorescent complex ability to physically crosslink, Au(I) sulfides tendency to form NIR (near-infrared) absorbing AuNPs compared to any similar work in literature. Syntheses of these hybrid nanomaterials has been thoroughly investigated and it is determined that either metallic nanoparticles syntheses or syntheses of phosphorescent hydrogels can be carried in single step without involving any hazardous reducing agents or crosslinkers or stabilizers that are commonly employed during multiple step syntheses protocols for syntheses of similar materials in literature. These astounding results that have been discovered within studies of hybrid nanomaterials are an asset to applications ranging from materials development to health science and will have striking effect on environmental and green chemistry approaches.
Biodegradable Poly(hydroxy Butyrate-co-valerate) Nanocomposites And Blends With Poly(butylene Adipate-co-terephthalate) For Sensor Applications
The utilization of biodegradable polymers is critical for developing “cradle to cradle” mindset with ecological, social and economic consequences. Poly(hydroxy butyrate-co-valerate) (PHBV) shows significant potential for many applications with a polypropylene equivalent mechanical performance. However, it has limitations including high crystallinity, brittleness, small processing window, etc. which need to be overcome before converting them into useful products. Further the development of biodegradable strain sensing polymer sensors for structural health monitoring has been a growing need. In this dissertation I utilize carbon nanotubes as a self sensing dispersed nanofiller. The impact of its addition on PHBV and a blend of PHBV with poly(butylene adipate-co-terephthalate) (PBAT) polymer was examined. Nanocomposites and blends of PHBV, PBAT, and MWCNTs were prepared by melt-blending. The effect of MWCNTs on PHBV crystallinity, crystalline phase, quasi-static and dynamic mechanical property was studied concurrently with piezoresistive response. In PHBV/PBAT blends a rare phenomenon of melting point elevation by the addition of low melting point PBAT was observed. The blends of these two semicrystalline aliphatic and aromatic polyesters were investigated by using differential scanning calorimetry, small angle X-ray scattering, dynamic mechanical analysis, surface energy measurement by contact angle method, polarized optical and scanning electron microscopy, and rheology. The study revealed a transition of immiscible blend compositions to miscible blend compositions across the 0-100 composition range. PHBV10, 20, and 30 were determined to be miscible blends based on a single Tg and rheological properties. The inter-relation between stress, strain, morphological structure and piezoresistive response of MWCNT filled PHBV and PHBV/PBAT blend system was thoroughly investigated. The outcomes of piezoreistivity study indicated MWCNT filled PHBV and PHBV/PBAT blend system as a viable technology for structural health monitoring. Finally, the compostability of pure polymer, blend system, and MWCNT filled system was studied indicating that PBAT and CNT decreased the biodegradability of PHBV ...
Bulk and Interfacial Effects on Density in Polymer Nanocomposites
The barrier properties of polymers are a significant factor in determining the shelf or device lifetime in polymer packaging. Nanocomposites developed from the dispersion of nanometer thick platelets into a host polymer matrix have shown much promise. The magnitude of the benefit on permeability has been different depending on the polymer investigated or the degree of dispersion of the platelet in the polymer. In this dissertation, the effect of density changes in the bulk and at the polymer-platelet interface on permeability of polymer nanocomposites is investigated. Nanocomposites of nylon, PET, and PEN were processed by extrusion. Montmorillonite layered silicate (MLS) in a range of concentrations from 1 to 5% was blended with all three resins. Dispersion of the MLS in the matrix was investigated by using one or a combination of X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Variation in bulk density via crystallization was analyzed using differential scanning calorimetry (DSC) and polarized optical microscopy. Interfacial densification was investigated using force modulation atomic force microscopy (AFM) and ellipsometry. Mechanical properties are reported. Permeability of all films was measured in an in-house built permeability measurement system. The effect of polymer orientation and induced defects on permeability was investigated using biaxially stretched, small and large cycle fatigue samples of PET and nylon nanocomposites. The effect of annealing in nylon and nanocomposites was also investigated. The measured permeability was compared to predicted permeability by considering the MLS as an ideal dispersion and the matrix as a system with concentration dependent crystallinity.
Carrier Mobility, Charge Trapping Effects on the Efficiency of Heavily Doped Organic Light-Emitting Diodes, and EU(lll) Based Red OLEDs
Transient electroluminescence (EL) was used to measure the onset of emission delay in OLEDs based on transition metal, phosphorescent bis[3,5-bis(2-pyridyl)-1,2,4-triazolato] platinum(ΙΙ) and rare earth, phosphorescent Eu(hfa)3 with 4'-(p-tolyl)-2,2":6',2" terpyridine (ttrpy) doped into 4,4'-bis(carbazol-9-yl) triphenylamine (CBP), from which the carrier mobility was determined. For the Pt(ptp)2 doped CBP films in OLEDs with the structure: ITO/NPB (40nm)/mcp (10nm)/65% Pt(ptp)2:CBP (25nm)/TPBI (30nm)/Mg:Ag (100nm), where NPB=N, N'-bis(1-naphthyl)-N-N'-biphenyl-1, 1'-biphenyl-4, MCP= N, N'-dicarbazolyl-3,5-benzene, TPBI=1,3,5-tris(phenyl-2-benzimidazolyl)-benzene, delayed recombination was observed and based on its dependence on frequency and duty cycle, ascribed to trapping and de-trapping processes at the interface of the emissive layer and electron blocker. The result suggests that the exciton recombination zone is at, or close to the interface between the emissive layer and electron blocker. The lifetime of the thin films of phosphorescent emitter Pt(ptp)2 were studied for comparison with rare earth emitter Eu(hfa)3. The lifetime of 65% Pt(ptp)2:CBP co-film was around 638 nanoseconds at the emission peak of 572nm, and the lifetime of neat Eu(hfa)3 film was obtained around 1 millisecond at 616 nm, which supports the enhanced efficiency obtained from the Pt(ptp)2 devices. The long lifetime and narrow emission of the rare earth dopant Eu(hfa)3 is a fundamental factor limiting device performance. Red organic light emitting diodes (OLEDs) based on the rare earth emitter Eu(hfa)3 with 4'-(p-tolyl)-2,2":6',2" terpyridine (ttrpy) complex have been studied and improved with respect performance. The 4.5% Eu(hfa)3 doped into CBP device produced the best power efficiency of 0.53 lm/W, and current efficiency of 1.09 cd/A. The data suggests that the long lifetime of the f-f transition of the Eu ion is a principal limiting factor irrespective of how efficient the energy transfer from the host to the dopant and the antenna effect are.
Characterization and Mechanical Properties of Nanoscale Precipitates in Modified Al-Si-Cu Alloys Using Transmission Electron Microscopy and 3D Atom Probe Tomography.
Among the commercial aluminum alloys, aluminum 319 (Al-7wt%Si-4wt%Cu) type alloys are popularly used in automobile engine parts. These alloys have good casting characteristics and excellent mechanical properties resulting from a suitable heat treatment. To get a high strength in the 319 type alloys, grain refining, reducing the porosity, solid solution hardening, and precipitation hardening are preferred. All experimental variables such as solidification condition, composition, and heat treatment are influence on the precipitation behavior; however, precipitation hardening is the most significant because excess alloying elements from supersaturated solid solution form fine particles which act as obstacles to dislocation movement. The challenges of the 319 type alloys arise due to small size of precipitate and complex aging response caused by multi components. It is important to determine the chemical composition, crystal structure, and orientation relationship as well as precipitate morphology in order to understand the precipitation behavior and strengthening mechanism. In this study, the mechanical properties and microstructure were investigated using transmission electron microscopy and three dimensional atom probe tomography. The Mn and Mg effects on the microstructure and mechanical properties are discussed with crystallographic study on the iron intermetallic phases. The microstructural evolution and nucleation study on the precipitates in the low-Si 319 type aluminum alloys are also presented with sample preparation and analysis condition of TEM and 3DAP tomography.
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 ...
Comparative Coarsening Kinetics of Gamma Prime Precipitates in Nickel and Cobalt Base Superalloys
The increasing technological need to push service conditions of structural materials to higher temperatures has motivated the development of several alloy systems. Among them, superalloys are an excellent candidate for high temperature applications because of their ability to form coherent ordered precipitates, which enable the retention of high strength close to their melting temperature. The accelerated kinetics of solute diffusion, with or without an added component of mechanical stress, leads to coarsening of the precipitates, and results in microstructural degradation, limiting the durability of the materials. Hence, the coarsening of precipitates has been a classical research problem for these alloys in service. The prolonged hunt for an alternative of nickel base superalloys with superior traits has gained hope after the recent discovery of Co-Al-W based alloys, which readily form high temperature g precipitates, similar to Ni base superalloys. In the present study, coarsening behavior of g precipitates in Co-10Al-10W (at. %) has been carried out at 800°C and 900°C. This study has, for the first time, obtained critical coarsening parameters in cobalt-base alloys. Apart from this, it has incorporated atomic scale compositional information across the g/g interfaces into classical Cahn-Hilliard model for a better model of coarsening kinetics. The coarsening study of g precipitates in Ni-14Al-7 Cr (at. %) has shown the importance of temporal evolution of the compositional width of the g/g interfaces to the coarsening kinetics of g precipitates. This study has introduced a novel, reproducible characterization method of crystallographic study of ordered phase by coupling of orientation microscopy with atom probe tomography (APT). Along with the detailed analysis of field evaporation behaviors of Ni and Co superalloys in APT, the present study determines the site occupancy of various solutes within ordered g precipitates in both Ni and Co superalloys. This study has explained the role of structural ...
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.
Definition of Brittleness: Connections Between Mechanical and Tribological Properties of Polymers.
The increasing use of polymer-based materials (PBMs) across all types of industry has not been matched by sufficient improvements in understanding of polymer tribology: friction, wear, and lubrication. Further, viscoelasticity of PBMs complicates characterization of their behavior. Using data from micro-scratch testing, it was determined that viscoelastic recovery (healing) in sliding wear is independent of the indenter force within a defined range of load values. Strain hardening in sliding wear was observed for all materials-including polymers and composites with a wide variety of chemical structures-with the exception of polystyrene (PS). The healing in sliding wear was connected to free volume in polymers by using pressure-volume-temperature (P-V-T) results and the Hartmann equation of state. A linear relationship was found for all polymers studied with again the exception of PS. The exceptional behavior of PS has been attributed qualitatively to brittleness. In pursuit of a precise description of such, a quantitative definition of brittleness has been defined in terms of the elongation at break and storage modulus-a combination of parameters derived from both static and dynamic mechanical testing. Furthermore, a relationship between sliding wear recovery and brittleness for all PBMs including PS is demonstrated. The definition of brittleness may be used as a design criterion in selecting PBMs for specific applications, while the connection to free volume improves also predictability of wear behavior.
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 ...
Design Principle on Carbon Nanomaterials Electrocatalysts for Energy Storage and Conversion
We are facing an energy crisis because of the limitation of the fossil fuel and the pollution caused by burning it. Clean energy technologies, such as fuel cells and metal-air batteries, are studied extensively because of this high efficiency and less pollution. Oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are essential in the process of energy storage and conversion, and noble metals (e.g. Pt) are needed to catalyze the critical chemical reactions in these devices. Functionalized carbon nanomaterials such as heteroatom-doped and molecule-adsorbed graphene can be used as metal-free catalysts to replace the expensive and scarce platinum-based catalysts for the energy storage and conversion. Traditionally, experimental studies on the catalytic performance of carbon nanomaterials have been conducted extensively, however, there is a lack of computational studies to guide the experiments for rapid search for the best catalysts. In addition, theoretical mechanism and the rational design principle towards ORR and OER also need to be fully understood. In this dissertation, density functional theory calculations are performed to calculate the thermodynamic and electrochemical properties of heteroatom-doped graphene and molecule-adsorbed graphene for ORR and OER. Gibb's free energy, overpotential, charge transfer and edge effect are evaluated. The charge transfer analysis show the positive charges on the graphene surface caused by the heteroatom, hetero-edges and the adsorbed organic molecules play an essential role in improving the electrochemical properties of the carbon nanomaterials. Based on the calculations, design principles are introduced to rationally design and predict the electrochemical properties of doped graphene and molecule-adsorbed graphene as metal-free catalysts for ORR and OER. An intrinsic descriptor is discovered for the first time, which can be used as a materials parameter for rational design of the metal-free catalysts with carbon nanomaterials for energy storage and conversion. The success of the design principle provides a better ...
Device Engineering for Enhanced Efficiency from Platinum(II) Phosphorescent OLEDs
Phosphorescent organic light emitting diodes (PHOLEDs) based on efficient electrophosphorescent dopant, platinum(II)-pyridyltriazolate complex, bis[3,5-bis(2-pyridyl)-1,2,4-triazolato]platinum(II) (Pt(ptp)2) have been studied and improved with respect to power efficiency, external efficiency, chromacity and efficiency roll-off. By studying the electrical and optical behavior of the doped devices and functionality of the various constituent layers, devices with a maximum EQE of 20.8±0.2 % and power efficiency of 45.1±0.9 lm/W (77lm/W with luminaries) have been engineered. This improvement compares to devices whose emission initially could only be detected by a photomultiplier tube in a darkened environment. These devices consisted of a 65 % bis[3,5-bis(2-pyridyl)-1,2,4-triazolato]platinum(II) (Pt(ptp)2) doped into 4,4'-bis(carbazol-9-yl)triphenylamine (CBP) an EML layer, a hole transporting layer/electron blocker of 1,1-bis[(di-4-tolylamino)phenyl]cyclohexane (TAPC), an electron transport layer of 1,3,5-tris(phenyl-2-benzimidazolyl)-benzene (TPBI), and a LiF/Al cathode. These devices show the acceptable range for warm white light quadrants and qualify to be called "warm white" even w/o adding another emissive layer. Dual EML devices composed of neat Pt(ptp)2 films emitting orange and CBP: Pt(ptp)2 film emitting blue-green produced a color rendering index (CRI) of 59 and color coordinates (CIE) of (0.47,0.49) at 1000Cd/m² with power efficiency of 12.6±0.2 lm/W and EQE of 10.8±0.2 %. Devices with two blue fluorescent emission layers as singlet filters and one broad yellow emission layer from CBP: Pt(ptp)2 displayed a CRI of 78 and CIE of (0.28,0.31) at 100Cd/m² with maximum power efficiency of 6.7±0.3 lm/W and EQE of 5.7±0.2 %.
Dynamic Adhesion and Self-cleaning Mechanisms of Gecko Setae and Spatulae
Geckos can freely climb on walls and ceilings against their body weight at speed of over 1ms-1. Switching between attachment and detachment seem simple and easy for geckos, without considering the surface to be dry or wet, smooth or rough, dirty or clean. In addition, gecko can shed dirt particles during use, keeping the adhesive pads clean. Mimicking this biological system can lead to a new class of dry adhesives for various applications. However, gecko’s unique dry self-cleaning mechanism remains unknown, which impedes the development of self-cleaning dry adhesives. In this dissertation we provide new evidence and self-cleaning mechanism to explain how gecko shed particles and keep its sticky feet clean. First we studied the dynamic enhancement observed between micro-sized particles and substrate under dry and wet conditions. The adhesion force of soft (polystyrene) and hard (SiO2 and Al2O3) micro-particles on soft (polystyrene) and hard (fused silica and sapphire) substrates was measured using an atomic force microscope (AFM) with retraction (z-piezo) speed ranging over 4 orders of magnitude. The adhesion is strongly enhanced by the dynamic effect. When the retraction speeds varies from 0.02 µm/s to 156 µm/s, the adhesion force increases by 10% ~ 50% in dry nitrogen while it increases by 15%~70% in humid air. A dynamic model was developed to explain this dynamic effect, which agrees well with the experimental results. Similar dynamic enhancement was also observed in aqueous solution. The influence of dynamic factors related to the adhesion enhancement, such as particle inertia, viscoelastic deformations and crack propagation, was discussed to understand the dynamic enhancement mechanisms. Although particles show dynamic enhancement, Gecko fabrillar hair shows a totally different trend. The pull off forces of a single gecko seta and spatula was tested by AFM under different pull-off velocities. The result shows that both the spatula and ...
Effects of Plasma, Temperature and Chemical Reactions on Porous Low Dielectric Films for Semiconductor Devices
Low-dielectric (k) films are one of the performance drivers for continued scaling of integrated circuit devices. These films are needed in microelectronic device interconnects to lower power consumption and minimize cross talk between metal lines that "interconnect" transistors. Low-k materials currently in production for the 45 and 65 nm node are most often organosilicate glasses (OSG) with dielectric constants near 2.8 and nominal porosities of 8-10%. The next generation of low-k materials will require k values 2.6 and below for the 45 nm device generation and beyond. The continuous decrease in device dimensions in ultra large scale integrated (ULSI) circuits have brought about the replacement of the silicon dioxide interconnect dielectric (ILD), which has a dielectric constant (k) of approximately 4.1, with low dielectric constant materials. Lowering the dielectric constant reduces the propagation delays, RC constant (R = the resistance of the metal lines; C = the line capacitance), and metal cross-talk between wires. In order to reduce the RC constants, a number of low-k materials have been studied for use as intermetal dielectrics. The k values of these dielectric materials can be lowered by replacing oxide films with carbon-based polymer films, incorporating hydrocarbon functional groups into oxide films (SiOCH films), or introducing porogens in the film during processing to create pores. However, additional integration issues such as damage to these materials caused by plasma etch, plasma ash, and wet etch processes are yet to be overcome. This dissertation reports the effects of plasma, temperature and chemical reactions on low-k SiOCH films. Plasma ash processes have been known to cause hydrophobic films to lose their hydrophobic methyl groups, rendering them to be hydrophilic. This allows the films to readily absorb moisture. Supercritical carbon dioxide (SC-CO2) can be used to transport silylating agents, hexamethyldisilazane (HMDS) and diethoxy-dimethlysilane (DEDMS), to functionalize the ...
Electrical and Structure Properties of High-κ Barium Tantalite and Aluminum Oxide Interface with Zinc Oxide for Applications in Transparent Thin Film Transistors
ZnO has generated interest for flexible electronics/optoelectronic applications including transparent thin film transistors (TFTs). For this application, low temperature processes that simultaneously yield good electrical conductivity and optical transparency and that are compatible with flexible substrates such as plastic, are of paramount significance. Further, gate oxides are a critical component of TFTs, and must exhibit low leakage currents and self-healing breakdown in order to ensure optimal TFTs switching performance and reliability. Thus, the objective of this work was twofold: (1) develop an understanding of the processing-structure-property relationships of ZnO and high-κ BaTa2O6 and Al2O3 (2) understand the electronic defect structure of BaTa2O6 /ZnO and Al2O3/ZnO interfaces and develop insight to how such interfaces may impact the switching characteristics (speed and switching power) of TFTs featuring these materials. Of the ZnO films grown by atomic layer deposition (ALD), pulsed laser deposition (PLD) and magnetron sputtering at 100-200 °C, the latter method exhibited the best combination of n-type electrical conductivity and optical transparency. These determinations were made using a combination of photoluminescence, photoluminescence excitation, absorption edge and Hall measurements. Metal-insulator-semiconductor devices were then fabricated with sputtered ZnO and high-κ BaTa2O6 and Al2O3 and the interfaces of high-κ BaTa2O6 and Al2O3 with ZnO were analyzed using frequency dependent C-V and G-V measurements. The insulator films were deposited at room temperature by magnetron sputtering using optimized processing conditions. Although the Al2O3 films exhibited a lower breakdown strength and catastrophic breakdown behavior compared to BaTa2O6/ZnO interface, the Al2O3/ZnO interface was characterized by more than an order of magnitude smaller density of interface traps and interface trapped charge. The BaTa2O6 films in addition were characterized by a significantly higher concentration of fixed oxide charge. The transition from accumulation to inversion in the Al2O3 MIS structure was considerably sharper, and occurred at less than one tenth of ...
Exceptional Properties in Friction Stir Processed Beta Titanium Alloys and an Ultra High Strength Steel
The penchant towards development of high performance materials for light weighting engineering systems through various thermomechanical processing routes has been soaring vigorously. Friction stir processing (FSP) - a relatively new thermomechanical processing route had shown an excellent promise towards microstructural modification in many Al and Mg alloy systems. Nevertheless, the expansion of this process to high temperature materials like titanium alloys and steels is restricted by the limited availability of tool materials. Despite it challenges, the current thesis sets a tone for the usage of FSP to tailor the mechanical properties in titanium alloys and steels. FSP was carried out on three near beta titanium alloys, namely Ti6246, Ti185 and Tiβc with increasing β stability index, using various tool rotation rates and at a constant tool traverse speed. Microstructure and mechanical property relationship was studied using experimental techniques such as SEM, TEM, mini tensile testing and synchrotron x-ray diffraction. Two step aging on Ti6246 had resulted in an UTS of 2.2GPa and a specific strength around 500 MPa m3/mg, which is about 40% greater than any commercially available metallic material. Similarly, FSP on an ultra-high strength steel―Eglin steel had resulted in a strength greater than 2GPa with a ductility close to 10% at around 4mm from the top surface of stir zone (SZ). Experimental techniques such as microhardness, mini-tensile testing and SEM were used to correlate the microstructure and properties observed inside SZ and HAZ's of the processed region. A 3D temperature modeling was used to predict the peak temperature and cooling rates during FSP. The exceptional strength ductility combinations inside the SZ is believed to be because of mixed microstructure comprised of various volume fractions of phases such as martensite, bainite and retained austenite.
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 ...
First Principles Calculations of the Site Substitution Behavior in Gamma Prime Phase in Nickel Based Superalloys
Nickel based superalloys have superior high temperature mechanical strength, corrosion and creep resistance in harsh environments and found applications in the hot sections as turbine blades and turbine discs in jet engines and gas generator turbines in the aerospace and energy industries. The efficiency of these turbine engines depends on the turbine inlet temperature, which is determined by the high temperature strength and behavior of these superalloys. The microstructure of nickel based superalloys usually contains coherently precipitated gamma prime (?) Ni3Al phase within the random solid solution of the gamma () matrix, with the ? phase being the strengthening phase of the superalloys. How the alloying elements partition into the and ? phases and especially in the site occupancy behaviors in the strengthening ? phases play a critical role in their high temperature mechanical behaviors. The goal of this dissertation is to study the site substitution behavior of the major alloying elements including Cr, Co and Ti through first principles based calculations. Site substitution energies have been calculated using the anti-site formation, the standard defect formation formalism, and the vacancy formation based formalism. Elements such as Cr and Ti were found to show strong preference for Al sublattice, whereas Co was found to have a compositionally dependent site preference. In addition, the interaction energies between Cr-Cr, Co-Co, Ti-Ti and Cr-Co atoms have also been determined. Along with the charge transfer, chemical bonding and alloy chemistry associated with the substitutions has been investigated by examining the charge density distributions and electronic density of states to explain the chemical nature of the site substitution. Results show that Cr and Co atoms prefer to be close by on either Al sublattice or on a Ni-Al mixed lattice, suggesting a potential tendency of Cr and Co segregation in the ? phase.
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 ...
Formation and Quantification of Corrosion Deposits in the Power Industry
The presence of deposits on the secondary side of pressurized water reactor (PWR) steam generator systems is one of the main contributors to the high maintenance costs of these generators. Formation and transport of corrosion products formed due to the presence of impurities, metals and metallic oxides in the secondary side of the steam generator units result in formation of deposits. This research deals with understanding the deposit formation and characterization of deposits by studying the samples collected from different units in secondary side system at Comanche Peak Steam Electric Station (CPSES). Fourier transform infrared spectrophotometry (FTIR), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) have been used for studying the phases, morphologies and compositions of the iron oxides formed at Unit 1 and Unit 2 of secondary side of steamgenerator systems. Hematite and magnetite were found to be the dominant phases of iron oxides present in the units. Fe, Cr, O, Ni, Si, Cl and Cu were found in samples collected from both the units. A qualitative method was developed to differentiate iron oxides using laser induced breakdown spectroscopy (LIBS) based on temporal response of iron oxides to a high power laser beam. A quantitative FTIR technique was developed to identify and quantify iron oxides present in the different components of the secondary side of the steam generator of CPSES. Amines are used in water treatment to control corrosion and fouling in pressurized water reactors. CPSES presently uses an amine combination of dimethylamine (DMA), hydrazine and morpholine to control the water chemistry. Along with the abovementioned amines, this study also focuses on corrosion inhibition mechanismsof a new amine DBU (1, 8-diazabicyclo [5.4.0] undec-7-ene). Electrochemical impedance spectroscopy and polarization curves were used to study the interaction mechanism between DBU solution and inconel alloys 600 and 690 at steamgenerator operating ...
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.
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.
Functionalization and characterization of porous low-κ dielectrics.
The incorporation of fluorine into SiO2 has been shown to reduce the dielectric constant of the existing materials by reducing the electrical polarizability. However, the incorporation of fluorine has also been shown to decrease film stability. Therefore, new efforts have been made to find different ways to further decrease the relative dielectric constant value of the existing low-k materials. One way to reduce the dielectric constant is by decreasing its density. This reduces the amount of polarizable materials. A good approach is increasing porosity of the film. Recently, fluorinated silica xerogel films have been identified as potential candidates for applications such as interlayer dielectric materials in CMOS technology. In addition to their low dielectric constants, these films present properties such as low refractive indices, low thermal conductivities, and high surface areas. Another approach to lower k is incorporating lighter atoms such as hydrogen or carbon. Silsesquioxane based materials are among them. However, additional integration issues such as damage to these materials caused by plasma etch, plasma ash, and wet etch processes are yet to be overcome. This dissertation reports the effects of triethoxyfluorosilane-based (TEFS) xerogel films when reacted with silylation agents. TEFS films were employed because they form robust silica networks and exhibit low dielectric constants. However, these films readily absorb moisture. Employing silylation reactions enhances film hydrophobicity and permits possible introduction of this film as an interlayer dielectric material. Also, this work describes the effects of SC-CO2 in combination with silylating agents used to functionalize the damaged surface of the ash-damaged MSQ films. Ashed MSQ films exhibit increased water adsorption and dielectric constants due to the carbon depletion and modification of the properties of the low-k material caused by interaction with plasma species. CO2 is widely used as a supercritical solvent, because of its easily accessible critical point, low ...
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.
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.
Growth, Structure and Tribological Properties of Atomic Layer Deposited Lubricious Oxide Nanolaminates
Friction and wear mitigation is typically accomplished by introducing a shear accommodating layer (e.g., a thin film of liquid) between surfaces in sliding and/or rolling contacts. When the operating conditions are beyond the liquid realm, attention turns to solid coatings. Solid lubricants have been widely used in governmental and industrial applications for mitigation of wear and friction (tribological properties). Conventional examples of solid lubricants are MoS2, WS2, h-BN, and graphite; however, these and some others mostly perform best only for a limited range of operating conditions, e.g. ambient air versus dry nitrogen and room temperature versus high temperatures. Conversely, lubricious oxides have been studied lately as good potential candidates for solid lubricants because they are thermodynamically stable and environmentally robust. Oxide surfaces are generally inert and typically do not form strong adhesive bonds like metals/alloys in tribological contacts. Typical of these oxides is ZnO. The interest in ZnO is due to its potential for utility in a variety of applications. To this end, nanolaminates of ZnO, Al2O3, ZrO2 thin films have been deposited at varying sequences and thicknesses on silicon substrates and high temperature (M50) bearing steels by atomic layer deposition (ALD). The top lubricious, nanocrystalline ZnO layer was structurally-engineered to achieve low surface energy {0002}-orientated grain that provided low sliding friction coefficients (0.2 to 0.3), wear factors (range of 10-7 to 10-8 mm3/Nm) and good rolling contact fatigue resistance. The Al2O3 was intentionally made amorphous to achieve the {0002} preferred orientation while {101}-orientated tetragonal ZrO2 acted as a high toughness/load bearing layer. It was determined that the ZnO defective structure (oxygen sub-stoichiometric with growth stacking faults) aided in shear accommodation by re-orientating the nanocrystalline grains where they realigned to create new friction-reducing surfaces. Specifically, high resolution transmission electron microscopy (HRTEM) inside the wear surfaces revealed in an increase in ...
Hydrophobic, fluorinated silica xerogel for low-k applications.
A new hydrophobic hybrid silica film was synthesized by introducing one silicon precursor (as modifiers) into another precursor (network former). Hybrid films have improved properties. Hydrolysis and condensation of dimethyldiethoxysilane (DMDES) (solvent (EtOH) to DMDES molar ratio R = 4, water to DMDES molar ratio r = 4, 0.01 N HCl catalyst) was analyzed using high-resolution liquid 29Si NMR. It was found that after several hours, DMDES hydrolyzed and condensed into linear and cyclic species. Films from triethoxyfluorosilane (TEFS) have been shown to be promising interlayer dielectric materials for future integrated circuit applications due to their low dielectric constant and high mechanical properties (i.e., Young's modulus (E) and hardness (H)). Co-condensing with TEFS, linear structures from DMDES hydrolysis and condensation reactions rendered hybrid films hydrophobic, and cyclic structures induced the formation of pores. Hydrophobicity characterized by contact angle, thermal stability by thermogravimetric analysis (TGA), Fourier transform Infrared spectroscopy (FTIR), contact angle, and dynamic secondary ion mass spectroscopy (DSIMS), dielectric constant determined by impedance measurement, and mechanical properties (E and H) determined by nanoindentation of TEFS and TEFS + DMDES films were compared to study the effect of DMDES on the TEFS structure. Hybrid films were more hydrophobic and thermally stable. DMDES incorporation affected the dielectric constant, but showed little enhancement of mechanical properties.
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. ...
The Influence of Ohmic Metals and Oxide Deposition on the Structure and Electrical Properties of Multilayer Epitaxial Graphene on Silicon Carbide Substrates
Graphene has attracted significant research attention for next generation of semiconductor devices due to its high electron mobility and compatibility with planar semiconductor processing. In this dissertation, the influences of Ohmic metals and high dielectric (high-k) constant aluminum oxide (Al2O3) deposition on the structural and electrical properties of multi-layer epitaxial graphene (MLG) grown by graphitization of silicon carbide (SiC) substrates have been investigated. Uniform MLG was successfully grown by sublimation of silicon from epitaxy-ready, Si and C terminated, 6H-SiC wafers in high-vacuum and argon atmosphere. The graphene formation was accompanied by a significant enhancement of Ohmic behavior, and, was found to be sensitive to the temperature ramp-up rate and annealing time. High-resolution transmission electron microscopy (HRTEM) showed that the interface between the metal and SiC remained sharp and free of macroscopic defects even after 30 min, 1430 °C anneals. The impact of high dielectric constant Al2O3 and its deposition by radio frequency (RF) magnetron sputtering on the structural and electrical properties of MLG is discussed. HRTEM analysis confirms that the Al2O3/MLG interface is relatively sharp and that thickness approximation of the MLG using angle resolved X-ray photoelectron spectroscopy (ARXPS) as well as variable-angle spectroscopic ellipsometry (VASE) is accurate. The totality of results indicate that ARXPS can be used as a nondestructive tool to measure the thickness of MLG, and that RF sputtered Al2O3 can be used as a (high-k) constant gate oxide in multilayer grapheme based transistor applications.
Integrated Computational and Experimental Approach to Control Physical Texture During Laser Machining of Structural Ceramics
The high energy lasers are emerging as an innovative material processing tool to effectively fabricate complex shapes on the hard and brittle structural ceramics, which previously had been near impossible to be machined effectively using various conventional machining techniques. In addition, the in-situ measurement of the thermo-physical properties in the severe laser machining conditions (high temperature, short time duration, and small interaction volume) is an extremely difficult task. As a consequence, it is extremely challenging to investigate the evolution of surface topography through experimental analyses. To address this issue, an integrated experimental and computational (multistep and multiphysics based finite-element modeling) approach was employed to understand the influence of laser processing parameters to effectively control the various thermo-physical effects (recoil pressure, Marangoni convection, and surface tension) during transient physical processes (melting, vaporization) for controlled surface topography (surface finish). The results indicated that the material lost due to evaporation causes an increase in crater depth of machined cavity, whereas liquid expulsion created by the recoil pressure increases the material pileup height around the lip of machined cavity, the major attributes of surface topography (roughness). Also, it was found that the surface roughness increased with increase in laser energy density and pulse rate (from 10 to 50Hz), and with the decrease in distance between two pulses (from 0.6 to 0.1mm) or the increase in lateral and transverse overlap (0, 17, 33, 50, 67, and 83%). The results of the computational model are also validated by experimental observations with reasonably close agreement.
Investigations in the Mechanism of Carbothermal Reduction of Yttria Stabilized Zirconia for Ultra-high Temperature Ceramics Application and Its Influence on Yttria Contained in It
Zirconium carbide (ZrC) is a high modulus ceramic with an ultra-high melting temperature and, consequently, is capable of withstanding extreme environments. Carbon-carbon composites (CCCs) are important structural materials in future hypersonic aircraft; however, these materials may be susceptible to degradation when exposed to elevated temperatures during extreme velocities. At speeds of exceeding Mach 5, intense heating of leading edges of the aircraft triggers rapid oxidation of carbon in CCCs resulting in degradation of the structure and probable failure. Environmental/thermal barrier coatings (EBC/TBC) are employed to protect airfoil structures from extreme conditions. Yttria stabilized zirconia (YSZ) is a well-known EBC/TBC material currently used to protect metallic turbine blades and other aerospace structures. In this work, 3 mol% YSZ has been studied as a potential EBC/TBC on CCCs. However, YSZ is an oxygen conductor and may not sufficiently slow the oxidation of the underlying CCC. Under appropriate conditions, ZrC can form at the interface between CCC and YSZ. Because ZrC is a poor oxygen ion conductor in addition to its stability at high temperatures, it can reduce the oxygen transport to the CCC and thus increase the service lifetime of the structure. This dissertation investigates the thermodynamics and kinetics of the YSZ/ZrC/CCC system and the resulting structural changes across multiple size scales. A series of experiments were conducted to understand the mechanisms and species involved in the carbothermal reduction of ZrO2 to form ZrC. 3 mol% YSZ and graphite powders were uniaxially pressed into pellets and reacted in a graphite (C) furnace. Rietveld x-ray diffraction phase quantification determined that greater fractions of ZrC were formed when carbon was the majority mobile species. These results were validated by modeling the process thermochemically and were confirmed with additional experiments. Measurements were conducted to examine the effect of carbothermal reduction on the bond lengths in ...
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 ...
Laser Surface Treatment of Amorphous Metals
Amorphous materials are used as soft magnetic materials and also as surface coatings to improve the surface properties. Furthermore, the nanocrystalline materials derived from their amorphous precursors show superior soft magnetic properties than amorphous counter parts for transformer core applications. In the present work, laser based processing of amorphous materials will be presented. Conventionally, the nanocrystalline materials are synthesized by furnace heat treatment of amorphous precursors. Fe-based amorphous/nanocrystalline materials due to their low cost and superior magnetic properties are the most widely used soft magnetic materials. However, achieving nanocrystalline microstructure in Fe-Si-B ternary system becomes very difficult owing its rapid growth rate at higher temperatures and sluggish diffusion at low temperature annealing. Hence, nanocrystallization in this system is achieved by using alloying additions (Cu and Nb) in the ternary Fe-Si-B system. Thus, increasing the cost and also resulting in reduction of saturation magnetization. laser processing technique is used to achieve extremely fine nanocrystalline microstructure in Fe-Si-B amorphous precursor. Microstructure-magnetic Property-laser processing co-relationship has been established for Fe-Si-B ternary system using analytical techniques. Laser processing improved the magnetic properties with significant increase in saturation magnetization and near zero coercivity values. Amorphous materials exhibit excellent corrosion resistance by virtue of their atomic structure. Fe-based amorphous materials are economical and due to their ease of processing are of potential interest to synthesize as coatings materials for wear and corrosion resistance applications. Fe-Cr-Mo-Y-C-B amorphous system was used to develop thick coatings on 4130 Steel substrate and the corrosion resistance of the amorphous coatings was improved. It is also shown that the mode of corrosion depends on the laser processing conditions. The microstructure evolution and the corrosion mechanisms operating are evaluated using post processing and post corrosion analysis.
Long Term Property Prediction of Polyethylene Nanocomposites
The amorphous fraction of semicrystalline polymers has long been thought to be a significant contributor to creep deformation. In polyethylene (PE) nanocomposites, the semicrystalline nature of the maleated PE compatibilizer leads to a limited ability to separate the role of the PE in the nanocomposite properties. This dissertation investigates blown films of linear low-density polyethylene (LLDPE) and its nanocomposites with montmorillonite-layered silicate (MLS). Addition of an amorphous ethylene propylene copolymer grafted maleic anhydride (amEP) was utilized to enhance the interaction between the PE and the MLS. The amorphous nature of the compatibilizer was used to differentiate the effect of the different components of the nanocomposites; namely the matrix, the filler, and the compatibilizer on the overall properties. Tensile test results of the nanocomposites indicate that the addition of amEP and MLS separately and together produces a synergistic effect on the mechanical properties of the neat PE Thermal transitions were analyzed using differential scanning calorimetry (DSC) to determine if the observed improvement in mechanical properties is related to changes in crystallinity. The effect of dispersion of the MLS in the matrix was investigated by using a combination of X-ray Diffraction (XRD) and Scanning Electron Microscopy (SEM). Mechanical measurements were correlated to the dispersion of the layered silicate particles in the matrix. The nonlinear time dependent creep of the material was analyzed by examining creep and recovery of the films with a Burger model and the Kohlrausch-Williams-Watts (KWW) relation. The effect of stress on the nonlinear behavior of the nanocomposites was investigated by analyzing creep-recovery at different stress levels. Stress-related creep constants and shift factors were determined for the material by using the Schapery nonlinear viscoelastic equation at room temperature. The effect of temperature on the tensile and creep properties of the nanocomposites was analyzed by examining tensile and creep-recovery behavior of ...
Low Temperature Polymeric Precursor Derived Zinc Oxide Thin Films
Zinc oxide (ZnO) is a versatile environmentally benign II-VI direct wide band gap semiconductor with several technologically plausible applications such as transparent conducting oxide in flat panel and flexible displays. Hence, ZnO thin films have to be processed below the glass transition temperatures of polymeric substrates used in flexible displays. ZnO thin films were synthesized via aqueous polymeric precursor process by different metallic salt routes using ethylene glycol, glycerol, citric acid, and ethylene diamine tetraacetic acid (EDTA) as chelating agents. ZnO thin films, derived from ethylene glycol based polymeric precursor, exhibit flower-like morphology whereas thin films derived of other precursors illustrate crack free nanocrystalline films. ZnO thin films on sapphire substrates show an increase in preferential orientation along the (002) plane with increase in annealing temperature. The polymeric precursors have also been used in fabricating maskless patterned ZnO thin films in a single step using the commercial Maskless Mesoscale Materials Deposition system.
Measurement of Lattice Strain and Relaxation Effects in Strained Silicon Using X-ray Diffraction and Convergent Beam Electron Diffraction
The semiconductor industry has decreased silicon-based device feature sizes dramatically over the last two decades for improved performance. However, current technology has approached the limit of achievable enhancement via this method. Therefore, other techniques, including introducing stress into the silicon structure, are being used to further advance device performance. While these methods produce successful results, there is not a proven reliable method for stress and strain measurements on the nanometer scale characteristic of these devices. The ability to correlate local strain values with processing parameters and device performance would allow for more rapid improvements and better process control. In this research, x-ray diffraction and convergent beam electron diffraction have been utilized to quantify the strain behavior of simple and complex strained silicon-based systems. While the stress relaxation caused by thinning of the strained structures to electron transparency complicates these measurements, it has been quantified and shows reasonable agreement with expected values. The relaxation values have been incorporated into the strain determination from relative shifts in the higher order Laue zone lines visible in convergent beam electron diffraction patterns. The local strain values determined using three incident electron beam directions with different degrees of tilt relative to the device structure have been compared and exhibit excellent agreement.
Mechanical behavior and performance of injection molded semi-crystalline polymers.
I have used computer simulations to investigate the behavior of polymeric materials at the molecular level. The simulations were performed using the molecular dynamics method with Lennard-Jones potentials defining the interactions between particles in the system. Significant effort was put into the creation of realistic materials on the computer. For this purpose, an algorithm was developed based on the step-wise polymerization process. The resulting computer-generated materials (CGMs) exhibit several features of real materials, such as molecular weight distribution and presence of chain entanglements. The effect of the addition of a liquid crystalline (LC) phase to the flexible matrix was also studied. The concentration and distribution of the second phase (2P) were found to influence the mechanical and tribological properties of the CGMs. The size of the 2P agglomerates was found to have negligible influence on the properties within the studied range. Moreover, although the 2P reinforcement increases the modulus, it favors crack formation and propagation. Regions of high LC concentration exhibit high probability of becoming part of the crack propagation path. Simulations of the tensile deformation under a uniaxial force have shown that the molecular deformation mechanisms developing in the material depend on several variables, such as the magnitude of the force, the force increase rate, and the level of orientation of the chains. Three-dimensional (3D) graphical visualization tools were developed for representation and analysis of the simulation results. These also present interesting educational possibilities. Computer simulations provide us information which is inaccessible experimentally. From the concomitant use of simulations and experiments, a better understanding of the molecular phenomena that take place during deformation of polymers has been established.
Mechanisms of Ordered Gamma Prime Precipitation in Nickel Base Superalloys
Commercial superalloys like Rene88DT are used in high temperature applications like turbine disk in aircraft jet engines due to their excellent high temperature properties, including strength, ductility, improved fracture toughness, fatigue resistance, enhanced creep and oxidation resistance. Typically this alloy's microstructure has L12-ordered precipitates dispersed in disordered face-centered cubic γ matrix. A typical industrially relevant heat-treatment often leads to the formation of multiple size ranges of γ¢ precipitates presumably arising from multiple nucleation bursts during the continuous cooling process. The morphology and distribution of these γ′ precipitates inside γ matrix influences the mechanical properties of these materials. Therefore, the study of thermodynamic and kinetic factors influencing the evolution of these precipitates and subsequent effects is both relevant for commercial applications as well as for a fundamental understanding of the underlying phase transformations. The present research is primarily focused on understanding the mechanism of formation of different generations of γ′ precipitates during continuous cooling by coupling scanning electron microscopy (SEM), energy filtered TEM and atom probe tomography (APT). In addition, the phase transformations leading to nucleation of γ′ phase has been a topic of controversy for decades. The present work, for the first time, gives a novel insight into the mechanism of order-disorder transformations and associated phase separation processes at atomistic length scales, by coupling high angle annular dark field (HAADF) - STEM imaging and APT. The results indicate that multiple competing mechanisms can operate during a single continuous cooling process leading to different generations of γ′ including a non-classical mechanism, operative at large undercoolings.
Microstructural Evolution and Mechanical Response of Materials by Design and Modeling
Mechanical properties of structural materials are highly correlated to their microstructure. The relationship between microstructure and mechanical properties can be established experimentally. The growing need for structural materials in industry promotes the study of microstructural evolution of materials by design using computational approaches. This thesis presents the microstructural evolution of two different structural materials. The first uses a genetic algorithm approach to study the microstructural evolution of a high-temperature nickel-based oxide-dispersion-strengthened (ODS) alloy. The chosen Ni-20Cr ODS system has nano Y2O3 particles for dispersion strengthening and submicron Al2O3 for composite strengthening. Synergistic effects through the interaction of small dispersoids and large reinforcements improved high-temperature strength. Optimization considered different weight factors on low temperature strength, ductility, and high temperature strength. Simulation revealed optimal size and volume fraction of dispersoids and reinforced particles. Ni-20Cr-based alloys were developed via mechanical alloying for computational optimization and validation. The Ni-20Cr-1.2Y2O3-5Al2O3 alloy exhibited significant reduction in the minimum creep rate (on the order of 10-9 s-1) at 800oC and 100 MPa. The second considers the microstructural evolution of AA 7050 alloy during friction stir welding (FSW). Modeling the FSW process includes thermal, material flow, microstructural and strength modeling. Three-dimensional material flow and heat transfer model was developed for friction stir welding process of AA 7050 alloy to predict thermal histories and extent of deformation. Peak temperature decreases with the decrease in traverse speed at constant advance per revolution, while the increase in tool rotation rate enhances peak temperature. Shear strain is higher than the longitudinal and transverse strain for lower traverse speed and tool rotation rate; whereas for higher traverse speed and tool rotation rate, shear and normal strain acquire similar values. Precipitation distribution simulation using TC-PRISMA predicts the presence of η' and η in the as-received AA 7050-T7451 alloy and mostly η in the friction ...
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.
Mist and Microstructure Characterization in End Milling Aisi 1018 Steel Using Microlubrication
Flood cooling is primarily used to cool and lubricate the cutting tool and workpiece interface during a machining process. But the adverse health effects caused by the use of flood coolants are drawing manufacturers' attention to develop methods for controlling occupational exposure to cutting fluids. Microlubrication serves as an alternative to flood cooling by reducing the volume of cutting fluid used in the machining process. Microlubrication minimizes the exposure of metal working fluids to the machining operators leading to an economical, safer and healthy workplace environment. In this dissertation, a vegetable based lubricant is used to conduct mist, microstructure and wear analyses during end milling AISI 1018 steel using microlubrication. A two-flute solid carbide cutting tool was used with varying cutting speed and feed rate levels with a constant depth of cut. A full factorial experiment with Multivariate Analysis of Variance (MANOVA) was conducted and regression models were generated along with parameter optimization for the flank wear, aerosol mass concentration and the aerosol particle size. MANOVA indicated that the speed and feed variables main effects are significant, but the interaction of (speed*feed) was not significant at 95% confidence level. The model was able to predict 69.44%, 68.06% and 42.90% of the variation in the data for both the flank wear side 1 and 2 and aerosol mass concentration, respectively. An adequate signal-to-noise precision ratio more than 4 was obtained for the models, indicating adequate signal to use the model as a predictor for both the flank wear sides and aerosol mass concentration. The highest average mass concentration of 8.32 mg/m3 was realized using cutting speed of 80 Surface feet per minute (SFM) and a feed rate of 0.003 Inches per tooth (IPT). The lowest average mass concentration of 5.91 mg/m3 was realized using treatment 120 SFM and 0.005 IPT. The ...
Nano-crystallization Inhibition in 5 Nm Ru Film Diffusion Barriers for Advanced Cu-interconnect
As the semiconductor industries are moving beyond 22 nm node technology, the currently used stacked Ta/TaN diffusion barrier including a copper seed will be unable to fulfill the requirements for the future technologies. Due to its low resistivity and ability to perform galvanic copper fill without a seed layer, ruthenium (Ru) has emerged as a potential copper diffusion barrier. However, its crystallization and columnar nanostructure have been the main cause of barrier failures even at low processing temperatures (300 oC -350 oC). In this study, we have proposed and evaluated three different strategies to improve the performance of the ultrathin Ru film as a diffusion barrier for copper. The first study focused on shallow surface plasma irradiation/amorphization and nitridation of 5 nm Ru films. Systematic studies of amorphization and nitrogen incorporation versus sample bias were performed. XPS, XRD and RBS were used to determine the physico-chemical, crystallization and barrier efficiency of the plasma modified Ru barrier. The nitrogen plasma surface irradiation of Ru films at substrate bias voltage of -350 V showed an improved barrier performance up to 400 oC annealing temperatures. The barrier barely started failing at 450 oC due mainly to nitrogen instability. The second study involved only amorphization of the Ru thin film without any nitrogen incorporation. A low energy ion beam irradiation/amorphization on Ru thin film was carried out by using 60 KeV carbon ions with different irradiation doses. The irradiation energy was chosen high enough so that the irradiation ions pass through the whole Ru thin film and stop in the SiO2/Si support substrate. The C-ion fluence of 5×1016 atoms/cm2 at 60 KeV made the Ru film near amorphous without changing its composition. XRD and RBS were used to determine the relationship between crystallization and barrier efficiency of the carbon irradiated Ru barrier. The amorphized ...
Phase Separation and Second Phase Precipitation in Beta Titanium Alloys
The current understanding of the atomic scale phenomenon associated with the influence of beta phase instabilities on the evolution of microstructure in titanium alloys is limited due to their complex nature. Such beta phase instabilities include phase separation and precipitation of nano-scale omega and alpha phases in the beta matrix. The initial part of the present study focuses on omega precipitation within the beta matrix of model binary titanium molybdenum (Ti-Mo) alloys. Direct atomic scale observation of pre-transition omega-like embryos in quenched alloys, using aberration-corrected high resolution scanning transmission electron microscopy and atom probe tomography (APT) was compared and contrasted with the results of first principles computations performed using the Vienna ab initio simulation package (VASP) to present a novel mechanism of these special class of phase transformation. Thereafter the beta phase separation and subsequent alpha phase nucleation in a Ti-Mo-Al ternary alloy was investigated by coupling in-situ high energy synchrotron x-ray diffraction with ex-situ characterization studies performed using aberration corrected transmission electron microscopy and APT to develop a deeper understanding of the mechanism of transformation. Subsequently the formation of the omega phase in the presence of simultaneous development of compositional phase separation within the beta matrix phase of a Ti-10V-6Cu (wt%) alloy during continuous cooling has been investigated using a combination of transmission electron microscopy and atom probe tomography. The results of these investigations provided novel insights into the mechanisms of solid-state transformations in metallic systems by capturing the earliest stages of nucleation at atomic to near atomic spatial and compositional resolution.
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 ...
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.
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 ...