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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 …
Structure and Low-temperature Tribology of Lubricious Nanocrystalline ZnO/Al2O3 Nanolaminates and ZrO2 Monofilms Grown by Atomic Layer Deposition
Currently available solid lubricants only perform well under a limited range of environmental conditions. Unlike them, oxides are thermodynamically stable and relatively inert over a broad range of temperatures and environments. However, conventional oxides are brittle at normal temperatures; exhibiting significant plasticity only at high temperatures (>0.5Tmelting). This prevents oxides' use in tribological applications at low temperatures. If oxides can be made lubricious at low temperatures, they would be excellent solid lubricants for a wide range of conditions. Atomic layer deposition (ALD) is a growth technique capable of depositing highly uniform and conformal films in challenging applications that have buried surfaces and high-aspect-ratio features such as microelectromechanical (MEMS) devices where the need for robust solid lubricants is sometimes necessary. This dissertation investigates the surface and subsurface characteristics of ALD-grown ZnO/Al2O3 nanolaminates and ZrO2 monofilms before and after sliding at room temperature. Significant enhancement in friction and wear performance was observed for some films. HRSEM/FIB, HRTEM and ancillary techniques (i.e. SAED, EELS) were used to determine the mechanisms responsible for this enhancement. Contributory characteristics and energy dissipation modes were identified that promote low-temperature lubricity in both material systems.
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.
State accountability ratings as related to district size and diversity.
All Texas school districts were examined to determine the relationship of district size and diversity to the accountability ratings of selected Texas school districts and the implications of including all data in the accountability rating system. Eight large districts and 12 small districts were matched demographically utilizing data from the 2003-2004 school year. Information from the Texas Education Agency was accessed over 2003-2004 and 2004-2005. The ratings were found to be lowered from Recognized to Academically Acceptable with the inclusion of these groups 6 out of 20 times. These findings indicate that the Texas accountability system, in its current structure, excludes certain students based upon race and economic status and is not in compliance with what the law intended. This study should be replicated on a larger scale to assess its validity for a larger sample of small districts. Equity among states should be examined to provide information for a nationwide accountability system.
Orientation, Microstructure and Pile-Up Effects on Nanoindentation Measurements of FCC and BCC Metals
This study deals with crystal orientation effect along with the effects of microstructure on the pile-ups which affect the nanoindentation measurements. Two metal classes, face centered cubic (FCC) and body centered cubic (BCC, are dealt with in the present study. The objective of this study was to find out the degree of inaccuracy induced in nanoindentation measurements by the inherent pile-ups and sink-ins. Also, it was the intention to find out how the formation of pile-ups is dependant upon the crystal structure and orientation of the plane of indentation. Nanoindentation, Nanovision, scanning electron microscopy, electron dispersive spectroscopy and electron backscattered diffraction techniques were used to determine the sample composition and crystal orientation. Surface topographical features like indentation pile-ups and sink-ins were measured and the effect of crystal orientation on them was studied. The results show that pile-up formation is not a random phenomenon, but is quite characteristic of the material. It depends on the type of stress imposed by a specific indenter, the depth of penetration, the microstructure and orientation of the plane of indentation. Pile-ups are formed along specific directions on a plane and this formation as well as the pile-up height and the contact radii with the indenter is dependant on the aforesaid parameters. These pile-ups affect the mechanical properties like elastic modulus and hardness measurements which are pivotal variables for specific applications in micro and nano scale devices.
Advanced Technology for Source Drain Resistance Reduction in Nanoscale FinFETs
Dual gate MOSFET structures such as FinFETs are widely regarded as the most promising option for continued scaling of silicon based transistors after 2010. This work examines key process modules that enable reduction of both device area and fin width beyond requirements for the 16nm node. Because aggressively scaled FinFET structures suffer significantly degraded device performance due to large source/drain series resistance (RS/D), several methods to mitigate RS/D such as maximizing contact area, silicide engineering, and epitaxially raised S/D have been evaluated.
Polyethylene-layered double hydroxide and montmorillonite nanocomposites: Thermal, mechanical and flame retardance properties.
The effect of incorporation two clays; layered double hydroxides (LDH) and montmorillonite layered silicates (MLS) in linear low density polyethylene (PE) matrix was investigated. MLS and LDH were added of 5, 15, 30 and 60 weight percent in the PE and compounded using a Brabender. Ground pellets were subsequently compression molded. Dispersion of the clays was analyzed using optical microscopy, SEM and XRD. Both the layered clays were immiscible with the PE matrix and agglomerates formed with increased clay concentration. The thermal properties were studied by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Both clays served as nucleation enhancers increasing recrystallization temperatures in the composites. Flame retarding properties were determined by using the flammability HVUL-94 system. LDH indicated better flame retarding properties than MLS for PE. The char structure was analyzed by environmental scanning electron microscopy. Mechanical properties were studied by tensile testing and Vickers microhardness testing apparatus.
Modifications of epoxy resins for improved mechanical and tribological performances and their effects on curing kinetics.
A commercial epoxy, diglycidyl ether of bisphenol-A, was modified by two different routes. One was the addition of silica to produce epoxy composites. Three different silane coupling agents, glycidyloxypropyl trimethoxy silane (GPS), -methacryloxypropyl trimethoxy silane (MAMS) and 3-mercaptopropyltriethoxy silane (MPS), were used as silica-surface modifiers. The effects of silica content, together with the effects of chemical surface treatment of silica, were studied. The results indicate that epoxy composites with silica exhibit mechanical and tribological properties as well as curing kinetics different than the pure epoxy. The optimum silica content for improved mechanical and tribological properties (low friction coefficient and wear rate) was different for each type of silane coupling agent. An unequivocal correlation between good mechanical and improved tribological properties was not found. Activation energy of overall reactions was affected by the addition of silica modified with MAMS and MPS, but not with GPS. The second route was modification by fluorination. A new fluoro-epoxy oligomer was synthesized and incorporated into a commercial epoxy by a conventional blending method. The oligomer functioned as a catalyst in the curing of epoxy and polyamine. Thermal stability of the blends decreased slightly at a high oligomer content. Higher wear resistance, lower friction coefficient and higher toughness were found with increasing oligomer content; thus in this case there was a correlation between good mechanical and improved tribological properties. The results indicated that increasing toughness and formation of a transfer film contribute to improved tribological performances.
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