This project sought to address six objectives, outlined below. The objectives were met through the completion of ten tasks. 1) Solidify the theoretical understanding of the binary CO2/H2O system at reaction temperatures and pressures. The thermodynamics of pH prediction have been improved to include a more rigorous treatment of non-ideal gas phases. However it was found that experimental attempts to confirm theoretical pH predictions were still off by a factor of about 1.8 pH units. Arrhenius experiments were carried out and the activation energy for carbonic acid appears to be substantially similar to sulfuric acid. Titration experiments have not yet confirmed or quantified the buffering or acid suppression effects of carbonic acid on biomass. 2) Modify the carbonic acid pretreatment severity function to include the effect of endogenous acid formation and carbonate buffering, if necessary. It was found that the existing severity functions serve adequately to account for endogenous acid production and carbonate effects. 3) Quantify the production of soluble carbohydrates at different reaction conditions and severity. Results show that carbonic acid has little effect on increasing soluble carbohydrate concentrations for pretreated aspen wood, compared to pretreatment with water alone. This appears to be connected to the release of endogenous …

Correlation between length scales in the field of magnetism has long been a topic of intensive study. The long-term desire is simple: to determine one theory that completely describes the magnetic behavior of matter from an individual atomic particle all the way up to large masses of material. One key piece to this puzzle is connecting the behavior of a material's domains on the nanometer scale with the magnetic properties of an entire large sample or device on the centimeter scale. In the first case study involving the FeSiAl thin films, contrast and spacing of domain patterns are clearly related to microstructure and stress. Case study 2 most clearly demonstrates localized, incoherent domain wall motion switching with field applied along an easy axis for a square hysteresis loop. In case study 3, axis-specific images of the complex Gd-Si-Ge material clearly show the influence of uniaxial anisotropy. Case study 4, the only study with the sole intent of creating domain structures for imaging, also demonstrated in fairly simple terms the effects of increasing stress on domain patterns. In case study 5, it was proven that the width of magnetoresistance loops could be quantitatively predicted using only MFM. When all of the …

This Final Report for Cooperative Agreement No. DE-FC22-95PC93052, the ''Development of Alternative Fuels and Chemicals from Synthesis Gas,'' was prepared by Air Products and Chemicals, Inc. (Air Products), and covers activities from 29 December 1994 through 31 July 2002. The overall objectives of this program were to investigate potential technologies for the conversion of synthesis gas (syngas), a mixture primarily of hydrogen (H{sub 2}) and carbon monoxide (CO), to oxygenated and hydrocarbon fuels and industrial chemicals, and to demonstrate the most promising technologies at the LaPorte, Texas Alternative Fuels Development Unit (AFDU). Laboratory work was performed by Air Products and a variety of subcontractors, and focused on the study of the kinetics of production of methanol and dimethyl ether (DME) from syngas, the production of DME using the Liquid Phase Dimethyl Ether (LPDME{trademark}) Process, the conversion of DME to fuels and chemicals, and the production of other higher value products from syngas. Four operating campaigns were performed at the AFDU during the performance period. Tests of the Liquid Phase Methanol (LPMEOH{trademark}) Process and the LPDME{trademark} Process were made to confirm results from the laboratory program and to allow for the study of the hydrodynamics of the slurry bubble column reactor …

Magnetic particle inspection (MPI) is a widely used nondestructive inspection method for aerospace applications essentially limited to experiment-based approaches. The analysis of MPI characteristics that affect sensitivity and reliability contributes not only reductions in inspection design cost and time but also improvement of analysis of experimental data. Magnetic particles are easily attracted toward a high magnetic field gradient. Selection of a magnetic field source, which produces a magnetic field gradient large enough to detect a defect in a test sample or component, is an important factor in magnetic particle inspection. In this work a finite element method (FEM) has been employed for numerical calculation of the MPI simulation technique. The FEM method is known to be suitable for complicated geometries such as defects in samples. This thesis describes the research that is aimed at providing a quantitative scientific basis for magnetic particle inspection. A new FEM solver for MPI simulation has been developed in this research for not only nonlinear reversible permeability materials but also irreversible hysteresis materials that are described by the Jiles-Atherton model. The material is assumed to have isotropic ferromagnetic properties in this research (i.e., the magnetic properties of the material are identical in all directions in …

The Flooding Predictor is an advanced process control strategy comprising a patented pattern-recognition methodology that identifies pre-flood patterns discovered to precede flooding events in distillation columns. The grantee holds a U.S. patent on the modeling system. The technology was validated at the Separations Research Program, The University of Texas at Austin under a grant from the U. S. Department of Energy, Inventions & Innovation Program. Distillation tower flooding occurs at abnormally high vapor and/or liquid rates. The loss in tray efficiencies is attributed to unusual behavior of liquid inventories inside the column leading to conditions of flooding of the space in between trays with liquid. Depending on the severity of the flood condition, consequences range from off spec products to equipment damage and tower shutdown. This non-intrusive pattern recognition methodology, processes signal data obtained from existing column instrumentation. Once the pattern is identified empirically, it is modeled and coded into the plant's distributed control system. The control system is programmed to briefly "unload" the tower each time the pattern appears. The unloading takes the form of a momentary reduction in column severity, e.g., decrease bottom temperature, reflux or tower throughput. Unloading the tower briefly at the pre-flood state causes long-term …

Synthesis and incorporation of functionalized materials continues to generate significant research interest in academia and in industry. If chosen correctly, a functional group when incorporated into a polymer can deliver enhanced properties, such as adhesion, water solubility, thermal stability, etc. The utility of these new materials has been demonstrated in drug-delivery systems, coatings, membranes and compatibilizers. Two approaches exist to functionalize a material. The desired moiety can be added to the monomer either before or after polymerization. The polymers used range from low glass transition temperature elastomers to high glass transition temperature, high performance materials. One industrial example of the first approach is the synthesis of Teflon(reg. sign). Poly(tetrafluoroethylene) (PTFE or Teflon(reg. sign)) is synthesized from tetrafluoroethylene, a functionalized monomer. The resulting material has significant property differences from the parent, poly(ethylene). Due to the fluorine in the polymer, PTFE has excellent solvent and heat resistance, a low surface energy and a low coefficient of friction. This allows the material to be used in high temperature applications where the surface needs to be nonabrasive and nonstick. This material has a wide spread use in the cooking industry because it allows for ease of cooking and cleaning as a nonstick coating on …

This report summarizes the first-year accomplishments of a three-year program to investigate the geologic controls of hydrocarbon occurrence in the southern Appalachian basin in eastern Tennessee, southwestern Virginia, eastern Kentucky, and southern West Virginia. The project: (1) employs the petroleum system approach to understand the geologic controls of hydrocarbons; (2) attempts to characterize the T-P parameters driving petroleum evolution; (3) attempts to obtain more quantitative definitions of reservoir architecture and identify new traps; (4) is working with USGS and industry partners to develop new play concepts and geophysical log standards for subsurface correlation; and (5) is geochemically characterizing the hydrocarbons (cooperatively with USGS). First-year results include: (1) meeting specific milestones (determination of thrust movement vectors, fracture analysis, and communicating results at professional meetings and through publication). All milestones were met. Movement vectors for Valley and Ridge thrusts were confirmed to be west-directed and derived from pushing by the Blue Ridge thrust sheet, and fan about the Tennessee salient. Fracture systems developed during Paleozoic, Mesozoic, and Cenozoic to Holocene compressional and extensional tectonic events, and are more intense near faults. Presentations of first-year results were made at the Tennessee Oil and Gas Association meeting (invited) in June, 2003, at a workshop …

Lutein and zeaxanthin are the only carotenoids accumulated in the macula of the human retina and are known as the macular pigments (MP). These pigments account for the yellow color of the macula and appear to play an important role in protecting against age-related macular degeneration (AMD). The uptake of lutein and zeaxanthin in human eyes is remarkably specific. It is likely that specific transport or binding proteins are involved. The objective is to determine whether transthyretin (TTR) is a transport protein in human plasma and could thus deliver lutein from the blood to the retina. In this study, they used a biosynthetic {sup 13}C-lutein tracer and gas chromatography-combustion interfaced-isotope ratio mass spectrometry (GCC-IRMS) to gain the requisite sensitivity to detect the minute amounts of lutein expected as a physiological ligand for human transthyretin. The biosynthetic {sup 13}C-labeled lutein tracer was purified from algae. Healthy women (n = 4) each ingested 1 mg of {sup 13}C-labeled lutein daily for 3 days and a blood sample was collected 24 hours after the final dose. Plasma TTR was isolated by retinol-binding protein (RBP)-sepharose affinity chromatography and extracted with chloroform. The {sup 13}C/{sup 12}C ratio in the TTR extract was measured by GCC-IRMS. …

As time progresses, the world is using up more of the planet's natural resources. Without technological advances, the day will eventually arrive when these natural resources will no longer be sufficient to supply all of the energy needs. As a result, society is seeing a push for the development of alternative fuel sources such as wind power, solar power, fuel cells, and etc. These pursuits are even occurring in the state of Iowa with increasing social pressure to incorporate larger percentages of ethanol in gasoline. Consumers are increasingly demanding that energy sources be more powerful, more durable, and, ultimately, more cost efficient. Fast Ionic Conducting (FIC) glasses are a material that offers great potential for the development of new batteries and/or fuel cells to help inspire the energy density of battery power supplies. This dissertation probes the mechanisms by which ions conduct in these glasses. A variety of different experimental techniques give a better understanding of the interesting materials science taking place within these systems. This dissertation discusses Nuclear Magnetic Resonance (NMR) techniques performed on FIC glasses over the past few years. These NMR results have been complimented with other measurement techniques, primarily impedance spectroscopy, to develop models that describe …

Traditionally soymilk has been made with whole soybeans; however, there are other alternative raw ingredients for making soymilk, such as soy flour or full-fat soy flakes. US markets prefer soymilk with little or no beany flavor. modifying the process or using lipoxygenase-free soybeans can be used to achieve this. Unlike the dairy industry, fat reduction in soymilk has been done through formula modification instead of by conventional fat removal (skimming). This project reports the process optimization for solids and protein extraction, flavor improvement and fat removal in the production of 5, 8 and 12 {sup o}Brix soymilk from full fat soy flakes and whole soybeans using the Takai soymilk machine. Proximate analyses, and color measurement were conducted in 5, 8 and 12 {sup o}Brix soymilk. Descriptive analyses with trained panelists (n = 9) were conducted using 8 and 12 {sup o}Brix lipoxygenase-free and high protein blend soy flake soymilks. Rehydration of soy flakes is necessary to prevent agglomeration during processing and increase extractability. As the rehydration temperature increases from 15 to 50 to 85 C, the hexanal concentration was reduced. Enzyme inactivation in soy flakes milk production (measured by hexanal levels) is similar to previous reports with whole soybeans milk …

The tethered, chiral, chelating diphosphine rhodium complex, which catalyzes the enantioselective hydrogenation of methyl-{alpha}-acetamidocinnamate (MAC), has the illustrated structure as established by {sup 31}P NMR and IR studies. Spectral and catalytic investigations also suggest that the mechanism of action of the tethered complex is the same as that of the untethered complex in solution. The rhodium complexes, [Rh(COD)H]{sub 4}, [Rh(COD){sub 2}]{sup +}BF{sub 4}{sup -}, [Rh(COD)Cl]{sub 2}, and RhCl{sub 3} {center_dot} 3H{sub 2}O, adsorbed on SiO{sub 2} are optimally activated for toluene hydrogenation by pretreatment with H{sub 2} at 200 C. The same complexes on Pd-SiO{sub 2} are equally active without pretreatments. The active species in all cases is rhodium metal. The catalysts were characterized by XPS, TEM, DRIFTS, and mercury poisoning experiments. Rhodium on silica catalyzes the hydrogenation of fluorobenzene to produce predominantly fluorocyclohexane in heptane and 1,2-dichloroethane solvents. In heptane/methanol and heptane/water solvents, hydrodefluorination to benzene and subsequent hydrogenation to cyclohexane occurs exclusively. Benzene inhibits the hydrodefluorination of fluorobenzene. In DCE or heptane solvents, fluorocyclohexane reacts with hydrogen fluoride to form cyclohexene. Reaction conditions can be chosen to selectively yield fluorocyclohexane, cyclohexene, benzene, or cyclohexane. The oxorhenium(V) dithiolate catalyst [-S(CH{sub 2}){sub 3}s-]Re(O)(Me)(PPh{sub 3}) was modified by linking it to …

With the continuous advancements in molecular biology and modern medicine, organic synthesis has become vital to the support and extension of those discoveries. The isolations of new natural products allow for the understanding of their biological activities and therapeutic value. Organic synthesis is employed to aid in the determination of the relationship between structure and function of these natural products. The development of synthetic methodologies in the course of total syntheses is imperative for the expansion of this highly interdisciplinary field of science. In addition to the practical applications of total syntheses, the structural complexity of natural products represents a worthwhile challenge in itself. The pursuit of concise and efficient syntheses of complex molecules is both gratifying and enjoyable.

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The long term goals of this research were to define the substrate oxidation pathways, the electron transport mechanisms, and the modes of energy conservation employed during the dissimilatory oxidation of sulfur practiced by various species of the thiobacilli. Specific adhesion of the thiobacilli to elemental sulfur was studied by electrical impedance, dynamic light scattering, laser Doppler velocimetry, and optical trapping methods. The conclusion is that the thiobacilli appear to express specific receptors that enable the bacteria to recognize and adhere to insoluble sulfur. The enzyme tetrathionate oxidase was purified from two species of the thiobacilli. Extensive structural and functional studies were conducted on adenosine 5'-phosphosulfate reductase purified from cell-free extracts of Thiobacillus denitrificans. The kinetic mechanism of rhodanese was studied.

Switchgrass (Panicum virgatum L.) is a native grass species to much of the US. It has shown great potential for use in production of fuel ethanol from cellulosic biomass (Lynd et al., 1991). Work in Alabama demonstrated very high dry matter yields can be achieved with switchgrass (Maposse et al. 1995) in the southeastern US. Therefore, this region is thought to be an excellent choice for development of a switchgrass cropping system where farmers can produce the grass for either biomass or forage. Another report has shown success with selection and breeding to develop high yielding germplasm from adapted cultivars and ecotypes of switchgrass (Moser and Vogel 1995). In the mid 1990s, however, there was little plant breeding effort for switchgrass with a potential for developing a cultivar for the southeast region. The main goal of the project was to develop adaptive, high-yielding switchgrass cultivars for use in cropping systems for bioenergy production in the southeastern US. A secondary objective was to assess the potential of alternate herbaceous species such as bermudagrass (Cynodon dactylon L.), bahiagrass (Paspalum notatum Flugge.), and napiergrass (Pennisetum purpureum Schumach.) that may compete with switchgrass for herbaceous bioenergy production in the southeast. During the conduct of …

Diet has been associated with varying cancer rates in human populations for many years, yet the causes of the observed variation in cancer patterns have not been adequately explained (Wynder et al. 1977). Along with the effect of diet on human cancer incidence is the strong evidence that mutations are the initiating events in the cancer process (Vogelstein et al. 1992). Foods, when heated, are a good source of genotoxic carcinogens that very likely are a cause for some of these events(Doll et al. 1981). These carcinogens fall into two chemical classes: heterocyclic aromatic amines (HAA) and polycyclic aromatic hydrocarbons (PAH). There is ample evidence that many of these compounds are complete carcinogens in rodents(El-Bayoumy et al. 1995; Ohgaki et al. 1991). Heterocyclic aromatic amines are among the most potent mutagenic substances ever tested in the Ames/Salmonella mutagenicity test (Wakabayashi et al. 1992). Both classes of carcinogen cause tumors in rodents at multiple sites, (El-Bayoumy et al. 1995; Ohgaki et al. 1991) many of which are common tumor sites in people on a Western diet. An HAA, PhIP (2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine), and a PAH, B[a]P (benzo[a]pyrene), of comparable carcinogenic potency caused mammary gland tumors in a feeding study in female rats (El-Bayoumy …

In this document, we describe the results of radiation damage testing and characterization for specimens that were resintered to re-establish crystallinity. The phases in these specimens have become amorphous from radiation induced damage over the 8 months since sintering.

Numerical simulation is an effective and economical tool for optimally designing laboratory experiments and deriving practical experimental conditions. We executed a detailed numerical simulation study to examine the active fracture concept (AFC, Liu et al., 1998) using a cubic meter-sized block model. The numerical simulations for this study were performed by applying various experimental conditions, including different bottom flow boundaries, varying injection rates, and different fracture-matrix interaction (by increasing absolute matrix permeability at the fracture matrix boundary) for a larger fracture interaction under transient or balanced-state flow regimes. Two conceptual block models were developed based on different numerical approaches: a two-dimensional discrete-fracture-network model (DFNM) and a one-dimensional dual continuum model (DCM). The DFNM was used as a surrogate for a natural block to produce synthetic breakthrough curves of water and tracer concentration under transient or balanced-state conditions. The DCM is the approach typically used for the Yucca Mountain Project because of its computational efficiency. The AFC was incorporated into the DCM to capture heterogeneous flow patterns that occur in unsaturated fractured rocks. The simulation results from the DCM were compared with the results from the DFNM to determine whether the DCM could predict the water flow and tracer transport observed …

The California Water Resources RESAC objectives were toutilize NASA data to provide state-of-the-art real-time and forecastinformation (observation and simulation) on hydroclimate, water quantityand quality, and runoff related hazards to water resources managers(e.g., NWS, CA Dept. of Water Resources, USBR), the insurance industry,emergency response agencies, policy decision-makers, and the generalpublic. In addition, the RESAC acts as an umbrella organization fosteringgrowing collaborations and partnerships. It was built on the foundationestablished through the U.S. Global Change Research Program and theNational and California Assessments. It is designed to support theongoing regional and national assessment process by improving ourunderstanding of specific regional features of the climate system and itsimpacts, and facilitating the dissemination of these results throughdata, publications, and outreach.The California Water Resources RESACproduces three types of regional climate products that are enhanced byincorporation of NASA satellite data: (1) short-term (2-3 day) weatherand streamflow forecasts, (2) seasonal hydroclimate, and (3) long-termclimate change scenarios and hydrologic impacts. Our team has built anexcellent record in providing quantitative precipitation and streamflowforecasts to the water resources and weather prediction communities. Wehave been working with scientists from various University of Californiainstitutions and government agencies to improve weather and streamflowpredictions and studies of regional hydroclimate, and its impacts onwater resources, the …

The aqueous cleaning parameter of interest in this series of studies was the pH of the aqueous cleaning solution. A sessile droplet of industrial quench oil was analyzed to determine the effect of varied solution pH its removal from a stainless steel surface.

Implementation of the work program of Budget Period 2 of the East Binger Unit (''EBU'') DOE Project continues. Significant advances with the reservoir simulation model have led to changes in the program. One planned horizontal well location, EBU 44-3H, has been eliminated from the program, and another, EBU 45-3H, has been deferred, and may be replaced by a vertical well or completely eliminated at a future date. A new horizontal well location, EBU 63-2H, has been added. EBU 74G-2, the one new injection well planned for the project, was completed and brought on production. It will be produced for a period of time before converting it to injection. Performance is exceeding expectations. Work also continued on projects aimed at increasing injection in the pilot area. EBU 65-1 was converted to injection service. The project to add compression and increase injection capacity at the nitrogen management facility is nearing completion. Additional producer-to-injector conversions will follow.

Results were repeatedly obtained that were consistent with a hypothesis proposed at the beginning of this program, i.e., due to Metal-Support Interactions (MSI), unique active sites can be created in the metal-support interfacial region to enhance activity and improve selectivity in certain types of reactions, especially those involving the hydrogenation of carbonyl and unsaturated C=C bonds. Higher turnover frequencies (TOF-molecule/s/site) and increased selectivity for C=O bond versus C=C bond hydrogenation was established in the hydrogenation reactions of: acetone, crotonaldehyde, acetophenone, phenylethanol, acetylcyclohexane, benzaldehyde, benzyl alcohol, phenylacetaldehyde and citral over Pt/TiO{sub 2} MSI catalysts. Higher rates of hydrogenation benzene, toluene and xylene could be obtained over certain supported Pt and Pd catalysts. Au/TiO{sub 2} catalysts were developed that were active for CO hydrogenation at subambient temperatures. The influence of support and metal crystallite size were established for the adsorption of H{sub 2}, CO and O{sub 2} on families of Pt and Pd catalysts.

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Successful operation of a continuous caster is based upon control of heat transfer in the mold. The mold slag is a key component in the success of continuous casting; however, the phenomena that occur in the gap between the shell and the mold are largely unknown as until recently there have been no techniques that allowed visualization and quantification of the solidification behavior of liquid slags. This has lead to slag design being an empirical science or art. Recently a new experimental technique, called Double Hot Thermocouple Technique (DHTT), was developed at Carnegie Mellon University that allowed the solidification behavior of a slag to be observed and quantified under conditions that simulate the thermal conditions that occur in steelmaking environments. This technique allows ladle, tundish and mold slags to be characterized under extreme conditions including those found between the mold wall and the growing shell of a continuous caster. Thus, a program is initiated, under this grant, to quantify and describe the phenomena that occur during the solidification of a slag in a steel mill environment. This will allow slag design to become an engineering science rather than an empirical exercise. The project deliverables were as follows: (1) The further …