Thermoplastic polyimides (TPIs) exhibit high glass transition temperatures (Tgs), which make them useful in high performance applications. Amorphous and semicrystalline TPIs show sub-Tg relaxations, which can aid in improving strength characteristics through energy absorption. The a relaxation of both types of TPIs indicates a cooperative nature. The semicrystalline TPI shows thermo-irreversible cold crystallization phenomenon. The polymer liquid crystal (PLC) used in the blends is thermotropic and with longitudinal molecular structure. The small heat capacity change (ACP) associated with the glass transition indicates the PLC to be rigid rod in nature. The PLC shows a small endotherm associated with the melting. The addition of PLC to the semicrystalline TPI does not significantly affect the Tg or the melting point (Tm). The cold crystallization temperature (Tc) increases with the addition of the PLC, indicating channeling phenomenon. The addition of PLC also causes a negative deviation of the ACP, which is another evidence for channeling. The TPI, PLC and their blends show high thermal stability. The semicrystalline TPI absorbs moisture; this effect decreases with the addition of the PLC. The absorbed moisture does not show any effect on the degradation. The addition of PLC beyond 30 wt.% does not result in an improvement …

Montmorillonite reinforced polymers are a new development in the area of nanocomposite materials. Since reinforcement of epoxy is important to the development of high strength adhesives and composite matrices, the introduction of montmorillonite to epoxy is of interest. Compositional effects on epoxy reactivity, on molecular relaxation, and on mechanical properties were investigated. Change in reactivity was determined by Differential Scanning Calorimetry. Tensile properties at room temperature indicated improved modulus and retention of strength of the epoxy matrix but a decreased elongation to failure. Depression of dry nanocomposite glass transition was observed for nanocomposites beyond 5% by weight montmorillonite. Samples that were saturated with water showed lower moduli due to the epoxy matrix. The greatest moisture absorption rate was found at 7%, the least at 3%.

Molecular reinforcement through in-situ polymerization of liquid crystalline epoxies (LCEs) and a non-liquid crystalline epoxy has been investigated. Three LCEs: diglycidyl ether of 4,4'-dihydroxybiphenol (DGE-DHBP) and digylcidyl ether of 4-hydroxyphenyl-4"-hydroxybiphenyl-4'-carboxylate (DGE-HHC), were synthesized and blended with diglycidyl ether of bisphenol F (DGEBP-F) and subsequently cured with anhydride and amine curing agents. Curing kinetics were determined using differential scanning calorimetry (DSC). Parameters for autocatalytic curing kinetics of both pure monomers and blended systems were determined. The extent of cure for both monomers was monitored by using Fourier transform infrared spectroscopy (FT-IR). The glass transitions were evaluated as a function of composition using DSC and dynamic mechanical analysis (DMA). The results show that the LC constituent affects the curing kinetics of the epoxy resin and that the systems are highly miscible. The effects of molecular reinforcement of DGEBP-F by DGE-DHBP and DGE-HHC were investigated. The concentration of the liquid crystalline moiety affects mechanical properties. Tensile, impact and fracture toughness tests results are evaluated. Scanning electron microscopy of the fracture surfaces shows changes in failure mechanisms compared to the pure components. Results indicate that mechanical properties of the blended samples are improved already at low concentration by weight of the LCE added into …

It has become increasingly important to remain on the cutting edge of technology for a company to remain competitive and survive in today's high-tech industries. To do this, a company needs various resources dedicated to this cause. One of these resources is the use of existing materials, as starting points, for which improved materials can be based. For this, a company must rely on the characterization of existing materials to bring that base technology into their company. Through this evaluation, the base materials properties can be obtained and a material with improved properties can be developed. There are many techniques that can be used in characterizing an existing material, but not every technique is required to obtain the desired goal. The techniques utilized depend upon the depth of identification required. This report summarizes several techniques utilized in the characterization of existing materials and provides some examples of evaluated products.

Hafnium and Zirconium based gate dielectrics are considered potential candidates to replace SiO2 or SiON as the gate dielectric in CMOS processing. Furthermore, the addition of nitrogen into this pseudo-binary alloy has been shown to improve their thermal stability, electrical properties, and reduce dopant penetration. Because CMOS processing requires high temperature anneals (up to 1050 °C), it is important to understand the diffusion properties of any metal associated with the gate dielectric in silicon at these temperatures. In addition, dopant penetration from the doped polysilicon gate into the Si channel at these temperatures must also be studied. Impurity outdiffusion (Hf, Zr) from the dielectric, or dopant (B, As, P) penetration through the dielectric into the channel region would likely result in deleterious effects upon the carrier mobility. In this dissertation extensive thermal stability studies of alternate gate dielectric candidates ZrSixOy and HfSixOy are presented. Dopant penetration studies from doped-polysilicon through HfSixOy and HfSixOyNz are also presented. Rutherford backscattering spectroscopy (RBS), heavy ion RBS (HI-RBS), x-ray photoelectron spectroscopy (XPS), high resolution transmission electron microscopy (HR-TEM), and time of flight and dynamic secondary ion mass spectroscopy (ToF-SIMS, D-SIMS) methods were used to characterize these materials. The dopant diffusivity is calculated by modeling …

We investigate some of the mechanical design factors of wafers and the effect on strength. Thin, solid, pre-stressed films are proposed as a means to improve the bulk mechanical properties of a wafer. Three-point bending was used to evaluate the laser scribe density and chemical processing effect on wafer strength. Drop and strike tests were employed to investigate the edge bevel profile effect on the mechanical properties of the wafer. To characterize the effect of thin films on strength, one-micron ceramic films were deposited on wafers using PECVD. Coated samples were prepared by cleaving and were tested using four-point bending. Film adhesion was characterized by notched four-point bending. RBS and FTIR were used to obtain film chemistry, and nanoindentation was used to investigate thin film mechanical properties. A stress measurement gauge characterized residual film stress. Mechanical properties of the wafers correlated to the residual stress in the film.

Scratch recovery is a desirable property of many polymer systems. The reason why some materials have demonstrated excellent scratch recovery while others do not has been a mystery. Explaining the scratch resistance based upon the hardness of a material or its crosslink density is incorrect. In this thesis, novel polymers were tested in an attempt to discover materials that show excellent scratch recovery - one of the most important parameters in determining the wear of a material. Several hypotheses were developed in an attempt to give an accurate picture of how the chemical structure of a polymer affects its scratch recovery. The results show that high scratch recovery is a complex phenomenon not solely dependent upon the presence of electronegative atoms such as fluorine.

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 …

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 …

The rheology of 1-8% hydroxypropyl cellulose (HPC) solutions has been studied in the temperature range of 20-45 degrees Celsius. The results showed that the relative viscosity at each HPC concentration decreases with increasing temperature. The relative viscosity decreases drastically at about 43 degrees Celsius due to a phase transition. The influence of anionic surfactant, sodium dodecylsulfate (SDS), induced gelation of a 2% HPC solution. The HPC solutions gelled at surfactant SDS concentrations ranging from 0.4 to 1.0 critical micelle concentration (CMC). The gelation of the HPC/SDS hydrogel is explained in the surfactant SDD - bridged HPC linear polymer chains. The complex viscosity - concentration profile was determined below the CMC of the SDS - water pair. The peak itself was a function of frequency indicating the presence of two relaxation times within the gelled network.

The electron emission characteristics of aluminum, molybdenum and carbon nanotubes were studied. The experiments were setup to study the emission behavior as a function of temperature and exposure to oxygen. Changes in the surface work function as a result of thermal annealing were monitored with low energy ultra-violet photoelectron spectroscopy for flat samples while field emission energy distributions were used on tip samples. The change in the field emission from fabricated single tips exposed to oxygen while in operation was measured using simultaneous Fowler-Nordheim plots and electron energy distributions. From the results a mechanism for the degradation in the emission was concluded. Thermal experiments on molybdenum and aluminum showed that these two materials can be reduced at elevated temperatures, while carbon nanotubes on the other hand show effects of oxidation. To purely reduce molybdenum a temperature in excess of 750 ºC is required. This temperature exceeds that allowed by current display device technology. Aluminum on the other hand shows reduction at a much lower temperature of at least 125 ºC; however, its extreme reactivity towards oxygen containing species produces re-oxidation. It is believed that this reduction is due to the outward diffusion of aluminum atoms through the oxide. Carbon nanotubes …

The thermally responsive hydroxypropyl cellulose (HPC) hydrogel nanoparticles have been synthesized and characterized. The HPC particles were obtained by chemically crosslinking collapsed HPC polymer chains in water-surfactant (dodecyltrimethylammonium bromide) dispersion above the lower critical solution temperature (LCST) of the HPC. The size distributions of microgel particles, measured by dynamic light scattering, have been correlated with synthesis conditions including surfactant concentration, polymer concentration, and reaction temperature. The swelling and phase transition properties of resultant HPC microgels have been analyzed using both static and dynamic light scattering techniques. By first making gel nanoparticles and then covalently bonding them together, we have engineered a new class of gels with two levels of structural hierarchy: the primary network is crosslinked polymer chains in each individual particle, while the secondary network is a system of crosslinked nanoparticles. The covalent bonding contributes to the structural stability of the nanostructured gels, while self-assembly provides them with crystal structures that diffract light, resulting in colors. By using N-isopropylacrylamide copolymer hydrogel nanoparticles, we have synthesized nanoparticle networks that display a striking iridescence like precious opal but are soft and flexible like gelatin. This is in contrast to previous colored hydrogels, which were created either by adding dyes or fluorescent, …

The purpose of these experiments was to determine the degradation mechanisms of molybdenum based field emitter arrays to oxygen exposures and to improve the overall reliability. In addition, we also evaluated the emission current stability of gold-coated field emitter arrays to oxygen exposures. oxygen at 1x10-6 torr was introduced into the chamber through a leak valve for different lengths of time and duty cycles. To ensure identical oxygen exposure and experimental measurement conditions, tips on half the area of the FEA were fully coated with gold and the other half were left uncoated. The emission current from the gold coated half was found to degrade much less than that from the uncoated half, in the presence of oxygen. Also in the absence of oxygen, the emission current recovery for the gold-coated side was much quicker than that for the uncoated side.

Particle contamination control is a critical issue for the semiconductor industry. In the near future, this industry will be concerned with the chemical identities of contaminant particles as small as 0.01 pm in size. Therefore, analytical techniques with both high chemical sensitivity and spatial resolution are required. Transmission electron microscopy (TEM) provides excellent spatial resolution and yields structural and compositional information. It is rarely used, however, due to the difficulty of sample preparation. The goals of this research are to promote the use of TEM as an ultrafine particle analysis tool by developing new sample preparation methods, and to exploit the new TEM techniques for analysis of particles in semiconductor processing fluids. A TEM methodology for the analysis of particulate contaminants in fluids with an elemental detectability limit as low as 0.1 part per trillion (ppt), and a particle concentration detectability limit as low as 1 particle/ml for particles greater than 0.2 pm was developed and successfully applied to the analysis of particles in HF, H202, de-ionized (DI) water, and on the surface of an electronic device. HF samples from three manufacturers were examined. For HF (B), the maximum particle concentration was 8.3 x 103 particles/ml. Both a viscous material …

Solvent suspensions of a high performance polymer, Polyamide-imide (PAI) are widely used in magnetic wire coatings. Here we investigate the effect that the introduction of montmorillonite (MMT) has on PAI. MMT was introduced into an uncured PAI suspension; the sample was then cured by step-wise heat treatment. Polarized optical microscopy was used to choose the best suitable MMT for PAI matrix and to study the distribution of MMT in PAI matrix. Concentration dependent dispersion effect was studied by x-ray diffraction (XRD) and was confirmed by Transmission electron microscopy (TEM). Differential scanning Calorimetry (DSC) and Thermogravimetric analysis (TGA) was used to study impact of MMT on glass transition temperature (Tg) and degradation properties of PAI respectively. Micro-hardness testing of PAI nanocomposites was also performed. A concentration dependent state of dispersion was obtained. The glass transition (Tg), degradation and mechanical properties were found to correlate to the state of dispersion.

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 …

Nanocomposites with expandable smectites such as montmorillonite layered silicates (MLS) in polymer matrices have attracted extensive application interest. Numerous MLS concentrations have been used with no particular justification. Here, we investigate the effects of MLS dispersion within the matrix and on mechanical performance. The latter is resolved through a three-prong investigation on rate dependent tensile results, time dependent creep results and the influence of a sharp notch in polypropylene (PP) nanocomposites. A fixed concentration of maleated polypropylene (mPP) was utilized as a compatibilizer between the MLS and non-polar PP. Analysis of transmission electron micrographs and X-ray diffraction patterns on the surface and below the surface of our samples revealed a unique skin-core effect induced by the presence of clay. Differential scanning calorimetric and polarized optical microscopic examination of spherulites sizes showed changes in nucleation and growth resulting from both the maleated PP compatibilizer and the MLS. These structural changes resulted in a tough nanocomposite, a concept not reported before in the PP literature. Nonlinear creep analysis of the materials showed two concentrations 3 and 5 % wt of PP, which reduced the compliance in the base PP. The use of thermal wave imaging allowed the identification of ductile failure among …

This problem in lieu of thesis report presents a study on gate electrode materials on high K dielectrics, including poly-SiGe and Ru. The stability of poly-SiGe in direct contact with Hf silicon-oxynitride (HfSiON) is studied by rapid thermal annealing (RTA), Rutherford backscattering spectrometry (RBS), X-ray photoelectron spectroscopy (XPS) and high resolution transmission electron microscopy (HRTEM). By performing a series of RTA treatments we found that as RTA thermal budgets reach 1050 C for 30s, the poly-SiGe layer begins to intermix with the HfSiON film, as observed by TEM. The maximum annealing condition for the Hf0.14Si0.23O0.46N0.17 film to remain stable in contact with poly-SiGe is 1050 C for 20s in high purity N2(99.9%) ambient. We also found that after 1000 C annealing for 60s in a nitrogen ambient, the poly-SiGe crystal phase structure was changed from a columnar structure to a large grain structure. For a metal gate, Ru was studied to determine N2annealing effects on sheet resistance of Ru sample electrodes and electrical characterization of Ru/HfSiOx/Si stack. Results show that a pure Ru metal gate is not a good choice for high k materials since it is hard to etch off, and different annealing conditions can cause large changes in …