Browsing by Subject "oxidation"
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Item A Finite Element Framework for Multiscale/Multiphysics Analysis of Structures with Complex Microstructures(2010-10-12) Varghese, JulianThis research work has contributed in various ways to help develop a better understanding of textile composites and materials with complex microstructures in general. An instrumental part of this work was the development of an object-oriented framework that made it convenient to perform multiscale/multiphysics analyses of advanced materials with complex microstructures such as textile composites. In addition to the studies conducted in this work, this framework lays the groundwork for continued research of these materials. This framework enabled a detailed multiscale stress analysis of a woven DCB specimen that revealed the effect of the complex microstructure on the stress and strain energy release rate distribution along the crack front. In addition to implementing an oxidation model, the framework was also used to implement strategies that expedited the simulation of oxidation in textile composites so that it would take only a few hours. The simulation showed that the tow architecture played a significant role in the oxidation behavior in textile composites. Finally, a coupled diffusion/oxidation and damage progression analysis was implemented that was used to study the mechanical behavior of textile composites under mechanical loading as well as oxidation. A parametric study was performed to determine the effect of material properties and the number of plies in the laminate on its mechanical behavior. The analyses indicated a significant effect of the tow architecture and other parameters on the damage progression in the laminates.Item Advanced Reduction Processes - A New Class of Treatment Processes(2012-10-19) Vellanki, Bhanu PrakashA new class of treatment processes called Advanced Reduction Processes (ARP) has been proposed. The ARPs combine activation methods and reducing agents to form highly reactive reducing radicals that degrade oxidized contaminants. Batch screening experiments were conducted to identify effective ARP by applying several combinations of activation methods (ultraviolet light, ultrasound, electron beam, microwaves) and reducing agents (dithionite, sulfite, ferrous iron, sulfide) to degradation of five target contaminants (perchlorate, nitrate, perfluorooctanoic acid, 2,4 dichlorophenol, 1,2 dichloroethane) at 3 pH levels (2.4, 7.0, 11.2). These experiments identified the combination of sulfite activated by ultraviolet light produced by a low pressure mercury vapor lamp as an effective ARP. More detailed kinetic experiments were conducted with nitrate and perchlorate as target compounds and nitrate was found to degrade more rapidly than perchlorate. The effects of pH, sulfite concentration, and light intensity on perchlorate and nitrate degradation were investigated. The effectiveness of the sulfite/UV-L treatment process improved with increasing pH for both perchlorate and nitrate.Item Applications of the thermodynamics of elastic, crystalline materials(Texas A&M University, 2006-10-30) Si, XiuhuaThe thermodynamic behaviors of multicomponent, elastic, crystalline solids under stress and electro-magnetic fields are developed, including the extension of Euler??????s equation, Gibbs equation, Gibbs-Duhem equation, the conditions to be expected at equilibrium, and an extension of the Gibbs phase rule. The predictions of this new phase rule are compared with experimental observations. The stress deformation behaviors of the single martensitic crystal with and without magnetic fields were studied with the stress deformation equation derived by Slattery and Si (2005). One coherent interfacial condition between two martensitic variants was developed and used as one boundary condition of the problem. The dynamic magnetic actuation process of the single crystal actuator was analyzed. The extension velocity and the actuation time of the single crystal actuator are predicted. The relationship between the external stress and the extension velocity and the actuation time with the presence of a large external magnetic field was studied. The extended Gibbs-Duhem equation and Slattery-Lagoudas stress-deformation expression for crystalline solids was used. Interfacial constraints on the elastic portion of stress for crystalline-crystalline interfaces and crystalline-fluids or crystallineamorphous solids interfaces were derived and tested by the oxidation on the exterior of a circular cylinder, one-sided and two-sided oxidation of a plate. An experiment for measuring solid-solid interface surface energies was designed and the silicon-silicon dioxide surface energy was estimated. A new generalized Clausius-Clapeyron equation has been derived for elastic crystalline solids as well as fluids and amorphous solids. Special cases are pertinent to coherent interfaces as well as the latent heat of transformation.Item Asphalt Oxidation Kinetics and Pavement Oxidation Modeling(2012-07-16) Jin, XinMost paved roads in the United States are surfaced with asphalt. These asphalt pavements suffer from fatigue cracking and thermal cracking, aggravated by the oxidation and hardening of asphalt. This negative impact of asphalt oxidation on pavement performance has not been considered adequately in pavement design. Part of the reason is that the process of asphalt oxidation in pavement is not well understood. This work focused on understanding the asphalt oxidation kinetics and on developing pavement oxidation model that predicts asphalt oxidation and hardening in pavement under environmental conditions. A number of asphalts were studied in laboratory condition. Based on kinetics data, a fast-rate ? constant-rate asphalt oxidation kinetics model was developed to describe the early nonlinear fast-rate aging period and the later constant-rate period of asphalt oxidation. Furthermore, reaction kinetics parameters for the fast-rate and constant-rate reactions were empirically correlated, leading to a simplified model. And the experimental effort and time to obtain these kinetics parameters were significantly reduced. Furthermore, to investigate the mechanism of asphalt oxidation, two antioxidants were studied on their effectiveness. Asphalt oxidation was not significantly affected. It was found that evaluation of antioxidant effectiveness based on viscosity only is not reliable. The asphalt oxidation kinetics model was incorporated into the pavement oxidation model that predicts asphalt oxidation in pavement. The pavement oxidation model mimics the oxidation process of asphalt in real mixture at pavement temperatures. A new parameter, diffusion depth, defined the oxygen diffusion region in the mastic. A field calibration factor accounted for the factors not considered in the model such as the effect of small aggregate particles on oxygen diffusion. Carbonyl area and viscosity of binders recovered from field cores of three pavements in Texas were measured and were used for model calibration and validation. Results demonstrated that the proposed model estimates carbonyl growth over time in pavement, layer-by-layer, quite well. Finally, this work can be useful for incorporating asphalt oxidation into a pavement design method that can predict pavement performance with time and for making strategic decisions such as optimal time for maintenance treatments.Item Biological Manganese Oxidation by Pseudomonas putida in Trickling Filters(2015-02-10) McKee, Kyle PatrickManganese (Mn) is considered a nuisance chemical in drinking water. Manganese causes problems with staining, foul odor, undesirable tastes, and can be corrosive to pipelines. The United States Environmental Protection Agency (US EPA) recommends a secondary maximum contaminant level for Mn below a concentration of 0.05 mg/L. Currently manganese contaminated water is typically treated using expensive and potentially harmful oxidizing agents. Biological treatment techniques have been researched as a viable alternative for removing undesired chemicals from drinking water. In this study, bench scale trickling filters were constructed to compare the Mn removal efficiency between biochemical and abiotic processes. Glass beads between three and five millimeters in diameter were used as the solid media in the trickling filters with and without inoculation of a Mn oxidizing bacterium, Pseudomonas putida. Manganese oxidation and removal was found to be significantly greater in trickling filters with Pseudomonas putida biofilms after startup times of only 48 hours. Mn oxidation in Pseudomonas putida inoculated trickling filters was up to 75% greater than non-inoculated filters. One dimensional advection dispersive models were formulated to describe the transport of Mn in trickling filter porous media. Using the data collected in the experiments, the model predicted that that an average of 10 mg/L of influent Mn (II) concentration can be decreased by 78.56% with a filter depth of only 10 cm. The rapid startup time and the high Mn removal capacity of trickling filters inoculated with Pseudomonas putida can potentially become a mainstream treatment system in conjunction with sand filters.Item Chemiluminescence and Ignition Delay Time Measurements of C9H20 Oxidation in O2-Ar Behind Reflected Shock Waves(2011-02-22) Rotavera, BrandonStemming from a continuing demand for fuel surrogates, composed of only a few species, combustion of high-molecular-weight hydrocarbons (>C5) is of scientific interest due to their abundance in petroleum-based fuels, which contain hundreds of different hydrocarbon species, used for military, aviation, and transportation applications. Fuel surrogate development involves the use of a few hydrocarbon species to replicate the physical, chemical, combustion, and ignition properties of multi-component petroleum-based fuels, enabling fundamental studies to be performed in a more controlled manner. Of particular interest are straight-chained, saturated hydrocarbons (n-alkanes) due to the high concentration of these species in diesel and jet fuels. Prior to integrating a particular hydrocarbon into a surrogate fuel formulation, its individual properties are to be precisely known. n-Nonane (n-C9H20) is found in diesel and aviation fuels, and its combustion properties have received only minimal consideration. The present work involves first measurements of n-C9H20 oxidation in oxygen (O2) and argon (Ar), which were performed under dilute conditions at three levels of equivalence ratio (phi = 0.5, 1.0, and 2.0) and fixed pressure near 1.5 atm using a shock tube. Utilizing shock waves, high-temperature, fixed-pressure conditions are created within which the fuel reacts, where temperature and pressure are calculated using 1D shock theory and measurement of shock velocity. Of interest were measurements of ignition times and species time-histories of the hydroxyl (OH*) radical intermediate. A salient pre-ignition feature was observed in fuel-lean, stoichiometric, and fuel-rich OH* species profiles. The feature at each equivalence ratio was observed above 1400 K with the time-of-initiation (post reflected-shock) showing dependence on phi as the initiation time shortened with increasing phi. Relative percentage calculations reveal that the fuel-rich condition produces the largest quantity of pre-ignition OH*. Ignition delay time measurements and corresponding activation energy calculations show that the phi = 1.0 mixture was the most reactive, while the phi = 0.5 condition was least reactive.Item Detection of oxidation in human serum lipoproteins(Texas A&M University, 2006-04-12) Myers, Christine LeeA method for the oxidation of lipoproteins in vitro was developed using the free radical initiator, 2,2?-azobis-(2-amidinopropane) dihydrochloride (AAPH). Following in vitro oxidation, the susceptibility to oxidation of the serum samples was studied using density gradient ultracentifugation and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS). Shifts in mean buoyant density of the lipoprotein particles, specifically low density lipoprotein (LDL) and high density lipoprotein (HDL), were observed in the density profile following centrifugation. The degree of shift in the density proved to be proportional to the extent of oxidation. Changes in apolipoproteins were studied with MALDI-TOF-MS. Observed variations in the mass spectra include m/z shifts due to chemical modifications and change in isoform distributions. The oxidation procedure and analysis techniques were applied to a clinical application to study the effects of table grape consumption on lipoprotein susceptibility to oxidation. The main objective of the research, to show feasibility that these methods could be used in a clinical setting, was achieved.Item Development and Characterization of Novel Biomaterials for Fabrication of Multilayered Vascular Grafts(2013-12-05) Dempsey, David KandellCurrent synthetic alternatives to autologous grafts have often failed in small diameter applications (<6 mm) due to their thrombogenicity and compliance mismatch of native vasculature. No known synthetic material is capable of providing a non-thrombogenic inner layer that promotes endothelial cell (EC) interactions while also providing sufficient compliance and burst pressure for long term success in vivo. We have developed a multilayer design with an inner thromboresistant poly(ethylene glycol) (PEG) hydrogel based on Scl2-2 proteins designed to promote rapid in situ endothelialization. The bioactive component is reinforced with an electrospun segmented polyurethane (SPU) layer with tunable mechanical properties to withstand physiological loading conditions. The modulating of electrospun parameters to influence graft architecture coupled with the tunability of SPU mechanical performance is expected to give rise to improved graft biomechanical properties. Unfortunately, this advantage was found to be limited to only one property at a time. To this end, we have developed a novel semi-IPN approach to expand the range of possible graft compliance and burst pressures in order to simultaneously achieve biomechanical properties that exceed autologous veins. In addition to matching biomechanical properties, probability of long term success is also dependent on the grafts retention of perfomance despite cell-mediated attack. Typically, in the case poly(ether urethanes) (PEUs) and poly(carbonate urethanes) (PCUs), oxidative stability is the primary focus in the development of biostable SPUs. We have characterized the biostability of several commercially available polyurethanes while simultaneously evaluating the predictive capabilities of two main in vitro test methods to optimize our graft?s design. Despite ensured long term performance through optimizing biostability, a permanent scaffold prevents vasoactivity, a key function of vasculature. We have taken a tissue engineering approach to restorate vasoactivity by evaluating a novel aromatic biodegradable poly(ester urethane) (PEsU) for the reinforcing layer of a tissue engineering vascular graft (TEVG). This PEsU was expected to degrade into safe byproducts given its design based on glycolic acid and ethylene glycol. Following characterization, the PEsU was determined to be a strong potential reinforcing layer of a potential TEVG design. In summary, we have improved small diameter grafts through a multilayer design approach. Our graft demonstrated favorable initial fabrication feasibility, promising in vivo testing, biomechanical properties exceeding autologous veins, and strong oxidative stability. Overall, we have optimized the reinforcing layer through improvement of biomechanical properties via modulated material chemistry, optimized biostability, and identification of a biodegradable component expected to allow for restored vasoactivity.Item How Physical and Chemical Properties Change Ice Nucleation Efficiency of Soot and Polyaromatic Hydrocarbon Particles(2012-10-19) Suter, Katie AnnHeterogeneous freezing processes in which atmospheric aerosols act as ice nuclei (IN) cause nucleation of ice crystals in the atmosphere. Heterogeneous nucleation can occur through several freezing mechanisms, including contact and immersion freezing. The mechanism by which this freezing occurs depends on the ambient conditions and composition of the IN. Aerosol properties change through chemical aging and reactions with atmospheric oxidants such as ozone. We have conducted a series of laboratory experiments using an optical microscope apparatus equipped with a cooling stage to determine how chemical oxidation changes the ability of atmospheric aerosols to act as IN. Freezing temperatures are reported for aerosols composed of fresh and oxidized soot and polyaromatic hydrocarbons (PAHs) including anthracene, phenanthrene, and pyrene. Our results show that oxidized soot particles initiate ice freezing events at significantly warmer temperatures than fresh soot, 3 ?C on average. All oxidized PAHs studied had significantly warmer freezing temperatures than fresh samples. The chemical changes presumably causing the improved ice nucleation efficiency were observed using Fourier Transform Infrared Spectroscopy with Horizontal Attenuated Total Reflectance (FTIR-HATR). The addition of C=O bonds at the surface of the soot and PAHs led to changes in freezing temperatures. Finally, we have used classical nucleation theory to derive heterogeneous nucleation rates for the IN compositions in this research. The overall efficiency of the IN can be compared in order of least efficient to most efficient: fresh phenanthrene, fresh anthracene, fresh soot, oxidized phenanthrene, fresh pyrene, oxidized anthracene, oxidized soot, and oxidized pyrene. Overall oxidation of aerosols increases their ability to act as IN. Our results suggest that oxidation processes facilitate freezing at warmer temperatures at a broader range of conditions on the atmosphere.Item Impact of Chemical States on the Effective Work Function of Metal Gate and High-kappa Dielectric Materials on Novel Heterostructures(2012-10-19) Coan, MaryAn experimental and theoretical approach is taken to determine the effect of a heterojunction on the effective work function in a metal/high-? gate stack, the characteristics of aqueous hydrochloric acid cleaned (aq-HCl) GaN surface and the interface between GaN and Al2O3, HfO2 and GaON. The investigation of the effect of a heterojunction on the effective work function in a metal/high-? gate stack found that when a Ge/Si heterostructure on silicon is lightly doped and sufficiently thin, the work function can be extracted in a manner similar to that for a simple silicon substrate. Modifications to the terraced oxide structure are proposed to remove oxidation effects of the alternate channel materials. The extracted work function of TiN with various thicknesses on HfSiO is found to be in agreement with that of TiN on a silicon substrate. X-ray and ultraviolet photoelectron spectroscopy are used to observe the interface electronic states at the GaN (0001) and Al2O3, HfO2 and GaON dielectric interfaces. The GaN is cleaned using aqueous HCl prior to thermal oxidation to form GaON and atomic layer deposition of Al2O3 and HfO2. This was followed by a post deposition anneal. The GaN/HfO2 and GaN/Al2O3 interfaces exhibited dipoles of 1.6 eV and 0.4 eV +/- 0.2 eV, respectively. It is determined that the formation of an interfacial layer at the GaN/HfO2 interface is the primary cause of the larger dipole. Due to the knowledge of the formation of an interfacial GaOx or GaON layer during atomic layer deposition of HfO2, a better understanding of the GaN/GaON interface is needed. To accomplish this task, the interface electronic states at the GaN(0001) and GaON interface are observed using X-ray and ultraviolet photoelectron spectroscopy (XPS and UPS). XPS and UPS analysis of the GaN/GaON interface resulted in the calculation of a -2.7 eV +/- 0.2 eV dipole assuming that the core level shifts are only representative of the GaN band bending at the interface. If it is assumed that the core level shifts are only due to the oxidation of GaN, then the exhibited dipole at the GaN/GaON interface is -1.8 eV +/- 0.2 eV. Results indicate that the observed dipole is primarily caused by the polarization of the GaN. A theoretical approach is taken to provide a more complete understanding of the underlying formation mechanisms of a GaON interfacial layer during atomic layer deposition of HfO2. First, density functional theory is used to calculate the interactions of oxygen and water with the Ga-face of GaN clusters. The GaN clusters could be used as testbeds for the actual Ga-face on GaN crystals of importance in electronics. The results reveal that the local spin plays an important role in these interactions. It is found that the most stable interactions of O2 and the GaN clusters results in the complete dissociation of the O2 molecule to form two Ga-O-Ga bonds, while the most stable interactions between a H2O molecule and the GaN clusters are the complete dissociation of one of the O-H bonds to form a Ga-O-H bond and a Ga-H bond. Second, density functional theory is used to calculate the interaction of the reactants used to deposit HfO2 and Al2O3 during atomic layer deposition with hydrolyzed Ga-face GaN clusters. The results suggest that while further research is needed in this area to grasp a better understanding of the interactions of Trimethylaluminum (TMA) or Tertrakis(EthylMethylAmino)Hafnium (TEMAH) with hydrolyzed GaN clusters, it is found that a Ga-N(CH3)(CH2CH3) bond can form during the deposition of HfO2 using ALD and TEMAH as the reactant without breaking the Hf-N bond. The formation of a Ga-N(CH3)(CH2CH3) bond is significant because with the introduction of water into the system, the methyl and ethylmethyl groups may react to form a Ga-N-O bond which is believed to be the interfacial oxide found during deposition of HfO2 using ALD on GaN. No Ga-C bond structure formed in any fully optimized stable structure when analyzing the interaction of TMA with hydrolyzed GaN.Item Improving the Flavor of Ground Beef by Selecting Trimmings from Specific Locations(2012-08-17) Harbison, Amanda 1989-We hypothesized that carcass subcutaneous fat location would affect sensory and quality traits. Five carcass fat sources were tested: brisket, chuck, plate, flank, and round. Ground beef was formulated using each fat source and extra-lean beef trim (>95% lean) to contain 80% lean trim and 20% fat trim. Patties (100 g) were evaluated for color, lipid oxidation, fatty acid composition and consumer evaluation. Flavor was analyzed using a Gas chromatography with mass spectrometry (GC/MS) on the headspace above a cooked (74 degrees C) patty in a heated (60 degrees C) 473 mL glass jar with a solid phase micro-extraction (SPME) fiber. Color, thiobarbituric acid reactive substance assay (TBARS), consumer sensory, and cook/freezer loss data showed no differences (P > 0.05) among carcass locations. Percentage stearic acid was lower (P = 0.044) in the brisket than in the chuck and flank. The brisket was higher in percentage cis-vaccenic acid (P = 0.016) and in the saturated fatty acid to monounsaturated fatty acid ratio (P = 0.018), and lower (P = 0.004) in the percentage of total saturated fatty acids than all other sources of subcutaneous fat. Butanedione was highest (P = 0.013) in the flank and plate fat. Brisket tended to be higher (P = 0.054) than flank, plate, and round in 1-octen-3-ol. Brisket was higher (P = 0.008) than chuck, flank, and round, but not different (P > 0.05) than plate in octanedione. Brisket was higher (P = 0.003) than all other sources for beefy aroma. Flank was higher (P = 0.047) than chuck and round for chemical aroma. Brisket was higher (P = 0.004) than all other sources except flank for floral aromas. Plate was higher (P = 0.029) than all other sources for heated oil aromas. For secondary aroma descriptor, round was higher (P < 0.001) than flank, plate, and chuck for dairy. While differences in some key fatty acids and aromatics existed among carcass locations, when the fat was diluted with a common lean source, fat source did not have a negative effect on sensory or quality traits. Therefore, formulating ground beef using subcutaneous fat from specific locations on a carcass may improve the beef aromatics without negatively affecting sensory or quality traits.Item Non-destructive radiocarbon and stable isotopic analyses of archaeological materials using plasma oxidation(Texas A&M University, 2005-11-01) Steelman, Karen LynnPlasma oxidation, an alternative to combustion, is shown to be a non-destructive method for obtaining radiocarbon dates on perishable organic artifacts. Electrically excited oxygen gently converts organic carbon to carbon dioxide. Radiocarbon measurements are then performed using accelerator mass spectrometry. Because only sub-milligram amounts of material are removed from an artifact over its exposed surface, no visible change in fragile materials has been observed, even under magnification. Materials in this study include: Third International Radiocarbon Intercomparison (TIRI) sample B (Belfast pine); Fourth International Radiocarbon Intercomparison (FIRI) optional samples; six different materials from a naturally mummified baby bundle from southwest Texas; and peyote from Shumla Caves, Texas, and Cuatro Ci??negas, Mexico. Continuing previous research in the Rowe laboratory, a primary application of plasma oxidation has been its use to date rock art at archaeological sites around the world. This dissertation includes dates for: Toca do Serrote da Bastiana, Brazil; Ignatievskaya Cave, Russia; partially buried megalithic monuments, Spain; Arnold/Tainter Cave, Wisconsin; and Little Lost River Cave No. 1, Idaho.Item Spectroscopical Analysis of Mechano-chemically Activated Surfaces(2012-10-19) Cooper, RodrigoMechano-chemical activation is fundamentally different than chemical activation in that energy is added to alter the state of bond energy instead of exciting electrons to produce a chemical reaction. Mechano-chemical activation has demonstrated to alter the chemical reaction and rates. There remains no development of a model to quantify the changes in reactions due to mechano-chemical activation. This research aims in expanding our understanding of the influence of mechanochemical activation methods. The dynamics and kinetics of mechano-chemically activated surfaces will be studied using x-ray spectroscopy methods. Mechano-chemical interactions can be quantified through the study of electron energies. X-ray spectroscopy is a useful method of analyzing and quantifying electron energy states. X-ray absorbance is used to study the valence state electron shells of iron undergone activation through sliding friction of naturally produced wax. In-situ x-ray photoemission spectroscopy is employed to instantaneously characterize single crystal tantalum samples of each principal crystallographic orientation during oxidation. Sliding friction of the naturally produced wax resulted in a reduction in the binding energy of the iron 2p electrons by approximately one electron-volt. This reduction in binding energy is attributed to ferrocene which is an organo-metallic alloy, Fe(C5H5)2. Mechanical strain of the crystal lattices of tantalum resulted in altered activation energies. Activation energy increased with the application of lattice strain. At increasing strain, oxide properties become more dependent on the lattice strain than the crystal orientation and temperature. A model system is developed incorporating mechanical strain into the prediction of activation energy and rates.Item The role of docosahexaenoic acid in mediating mitochondrial membrane lipid peroxidation and apoptosis in colonocytes.(Texas A&M University, 2005-11-01) Ng, Yee VoonColon cancer is the second leading cause of cancer death in the United States. Epidemiological data indicate that the consumption of dietary fiber and fish/marine products favorably modulate colon tumorigenesis. Docosahexaenoic acid (DHA, 22:6n-3) from fish oil, and butyrate, a fiber fermentation product generated in colon, protect against colon tumorigenesis in part by inducing apoptosis. We have shown that DHA is incorporated into mitochondrial membrane phospholipids, which enhances oxidative stress and mitochondrial membrane potential (MP) dissipation. To elucidate the subcellular origin of oxidation induced by DHA and butyrate exposure, young adult mouse colonocytes (YAMC) were treated with 0200 ??M DHA, linoleic acid (LA, 18:2n-6) or no fatty acid (control) for 72 h with or without 5 mM butyrate for the final 6-24 h. Real time analysis of cellular membrane lipid oxidation, as indicated by oxidation of a lipophilic vital dye, mitochondrial permeability transition (MPT), as characterized by MP dissipation, and cytosolic ROS production, as depicted by hydrophilic ROS reactive fluorophore accumulation, were measured by living cell fluorescence microscopy. After 24 h of butyrate treatment, DHA primed cells showed a 29% increase in lipid oxidation (p<0.01), compared to no butyrate treatment, which could be blocked by a mitochondria targeted antioxidant, MitoQ (p <0.05), whereas LA treatment did not show an effect. In the absence of butyrate, DHA treatment, compared to LA, increased resting MP by 14% (p <0.01). In addition, butyrate-induced MP dissipation was greater (20%) in DHA primed cells as compared to LA (10%). This effect was blocked by pre-incubation with MPT inhibitors, cyclosporin A or bongkrekic acid at 1 ??M. These data suggest an increase in mitochondrial lipid oxidation and the resultant change in MP may contribute to the induction of apoptosis by DHA with butyrate as shown previously.Item Thermomechanical Constitutive Modeling of Viscoelastic Materials undergoing Degradation(2012-07-16) Karra, SatishMaterials like asphalt, asphalt concrete and polyimides that are used in the transportation and aerospace industry show viscoelastic behavior. These materials in the working environment are subject to degradation due to temperature, diffusion of moisture and chemical reactions (for instance, oxidation) and there is need for a good understanding of the various degradation mechanisms. This work focuses on: 1) some topics related to development of viscoelastic fluid models that can be used to predict the response of materials like asphalt, asphalt concrete, and other geomaterials, and 2) developing a framework to model degradation due to the various mechanisms (such as temperature, diffusion of moisture and oxidation) on polyimides that show nonlinear viscoelastic solid-like response. Such a framework can be extended to model similar degradation phenomena in the area of asphalt mechanics and biomechanics. The thermodynamic framework that is used in this work is based on the notion that the 'natural configuration' of a body evolves as the body undergoes a process and the evolution is determined by maximizing the rate of entropy production. The Burgers' fluid model is known to predict the non-linear viscoelastic fluid-like response of asphalt, asphalt concrete and other geomaterials. We first show that different choices for the manner in which the body stores energy and dissipates energy and satisfies the requirement of maximization of the rate of entropy production that leads to many three dimensional models. All of these models, in one dimension, reduce to the model proposed by Burgers. A thermodynamic framework to develop rate-type models for viscoelastic fluids which do not possess instantaneous elasticity (certain types of asphalt show such a behavior) is developed next. To illustrate the capabilities of such models we make a specific choice for the specific Helmholtz potential and the rate of dissipation and consider the creep and stress relaxation response associated with the model. We then study the effect of degradation and healing due to the diffusion of a fluid on the response of a solid which prior to the diffusion can be described by the generalized neo-Hookean model. We show that a generalized neo-Hookean solid - which behaves like an elastic body (i.e., it does not produce entropy) within a purely mechanical context - creeps and stress relaxes when infused with a fluid and behaves like a body whose material properties are time dependent. A framework is then developed to predict the viscoelastic response of polyimide resins under different temperature conditions. The developed framework is further extended to model the phenomena of swelling due to diffusion of a fluid through a viscoelastic solid using the theory of mixtures. Finally, degradation due to oxidation is incorporated into such a framework by introducing a variable that represents the extent of oxidation. The data from the resulting models are shown to be in good agreement with the experiments for polyimide resins.Item Tribo-electrochemical Characterization of Tantalum during Electrochemical-Mechanical Polishing (ECMP)(2012-02-14) Gao, FengElectrochemical Mechanical Polishing (ECMP) has become increasingly important due to the continuous decrease of the device size in integrated circuit (IC) fabrication. Tantalum (Ta) is a promising material as a substitute for copper in ICs. This dissertation studies the tribology and electrochemistry of Ta ECMP. The present research uses experimental combined analysis approaches. A specially designed experimental setup assembling a tribometer and a potentiostat was used to carry out Ta ECMP. The friction force and electrochemical reactions were measured simultaneously. Using this setup, we found the factors which affected the frictional behaviors of Ta during ECMP. The technique of single frequency electrochemical impedance spectroscopy (EIS) was employed to investigate the material removal mechanisms in Ta ECMP. The results presented the competing mechanisms of removal and formation of a surface oxide layer of Ta. In order to further the investigation in a nanoscale, the atomic force microscope (AFM) was used to measure the material removal rate. The Preston equation for the Ta ECMP was established. A new methodology was developed to study the oxidation state and process of Ta during ECMP. Through comparing the material removal rate measured by using the AFM and the calculated one via the Faraday?s law, the distribution of the Ta suboxides and pentoxide, as well as the oxidation process, was revealed. The oxidation process was strongly dependent of the applied anodic potential, thickness of the oxide layer, mechanical forces, and surface orientation. A polymer environmental cell was designed and produced. Using this cell and AFM, it was found that the material removal in the nanometer scale was a function of the surface orientations. This research is beneficial for optimization of the Ta ECMP process. This dissertation includes six chapters. After Introduction and Motivation and Objectives, the material, setup, and testing conditions are discussed in Chapter III. Chapter IV discusses the tribology and material removal mechanisms in Ta ECMP, while Chapter V the oxidation of Ta during ECMP, followed by Conclusions and Future Work.