None

An improved chemical kinetic model for the toluene oxidation based on experimental data obtained in a premixed laminar low-pressure flame with vacuum ultraviolet (VUV) photoionization and molecular beam mass spectrometry (MBMS) techniques has been proposed. The present mechanism consists of 273 species up to chrysene and 1740 reactions. The rate constants of reactions of toluene, decomposition, reaction with oxygen, ipso-additions and metatheses with abstraction of phenylic H-atom are updated; new pathways of C{sub 4} + C{sub 2} species giving benzene and fulvene are added. Based on the experimental observations, combustion intermediates such as fulvenallene, naphtol, methylnaphthalene, acenaphthylene, 2-ethynylnaphthalene, phenanthrene, anthracene, 1-methylphenanthrene, pyrene and chrysene are involved in the present mechanism. The final toluene model leads to an overall satisfactory agreement between the experimentally observed and predicted mole fraction profiles for the major products and most combustion intermediates. The toluene depletion is governed by metathese giving benzyl radicals, ipso-addition forming benzene and metatheses leading to C{sub 6}H{sub 4}CH{sub 3} radicals. A sensitivity analysis indicates that the unimolecular decomposition via the cleavage of a C-H bond has a strong inhibiting effect, while decomposition via C-C bond breaking, ipso-addition of H-atom to toluene, decomposition of benzyl radicals and reactions related to C{sub 6}H{sub …

Preliminary studies in the EM-21 Alternative Chemical Cleaning Program have focused on understanding the dissolution of Hematite (a primary sludge heel phase) in oxalic acid, with a focus on minimizing oxalic acid usage. Literature reviews, thermodynamic modeling, and experimental results have all confirmed that pH control, preferably using a supplemental proton source, is critical to oxalate minimization. With pH control, iron concentrations as high as 0.103 M have been obtained in 0.11 M oxalic acid. This is consistent with the formation of a 1:1 (iron:oxalate) complex. The solubility of Hematite in oxalic acid has been confirmed to increase by a factor of 3 when the final solution pH decreases from 5 to below 1. This is consistent with literature predictions of a shift in speciation from a 1:3 to 1:1 as the pH is lowered. Above a solution pH of 6, little Hematite dissolves. These results emphasize the importance of pH control in optimizing Hematite dissolution in oxalic acid.

None

Supplemental validation data has been generated that will be used to determine the applicability of the current Defense Waste Processing Facility (DWPF) liquidus temperature (T{sub L}) model to expanded DWPF glass regions of interest based on higher waste loadings. For those study glasses which had very close compositional overlap with the model development and/or model validation ranges (except TiO{sub 2} and MgO concentrations), there was very little difference in the predicted and measured TL values, even though the TiO{sub 2} contents were above the 2 wt% upper limit. The results indicate that the current T{sub L} model is applicable in these compositional regions. As the compositional overlap between the model validation ranges diverged from the target glass compositions, the T{sub L} data suggest that the model under-predicted the measured values. These discrepancies imply that there are individual oxides or their combinations that were outside of the model development and/or validation range over which the model was previously assessed. These oxides include B{sub 2}O{sub 3}, SiO{sub 2}, MnO, TiO{sub 2} and/or their combinations. More data is required to fill in these anticipated DWPF compositional regions so that the model coefficients could be refit to account for these differences.

We examine four Richtmyer-Meshkov (RM) experiments on shock-generated turbulent mix and find them to be in good agreement with our earlier simple model in which the growth rate h of the mixing layer following a shock or reshock is constant and given by 2{alpha}A{Delta}v, independent of initial conditions h{sub 0}. Here A is the Atwood number ({rho}{sub B}-{rho}{sub A})/({rho}{sub B} + {rho}{sub A}), {rho}{sub A,B} are the densities of the two fluids, {Delta}V is the jump in velocity induced by the shock or reshock, and {alpha} is the constant measured in Rayleigh-Taylor (RT) experiments: {alpha}{sup bubble} {approx} 0.05-0.07, {alpha}{sup spike} {approx} (1.8-2.5){alpha}{sup bubble} for A {approx} 0.7-1.0. In the extended model the growth rate beings to day after a time t*, when h = h*, slowing down from h = h{sub 0} + 2{alpha}A{Delta}vt to h {approx} t{sup {theta}} behavior, with {theta}{sup bubble} {approx} 0.25 and {theta}{sup spike} {approx} 0.36 for A {approx} 0.7. They ascribe this change-over to loss of memory of the direction of the shock or reshock, signaling transition from highly directional to isotropic turbulence. In the simplest extension of the model h*/h{sub 0} is independent of {Delta}v and depends only on A. They find that h*/h{sub …

Experiments conducted using a 200TW 60 fs laser have demonstrated up to 720 MeV electrons in the self-guided laser wakefield regime using pure Helium gas jet targets. Charge and energy of the accelerated electrons was measured using an electron spectrometer with a 0.5T magnet and charge callibrated image plates. The self-trapped charge in a helium plasma was shown to fall off with decreasing electron density with a threshold at 2.5 x 10{sup 18} (cm{sup -3}) below which no charge is trapped. Self-guiding however is shown to continue below this density limitation over distances of 14 mm with an exit spot size of 25{micro}m. Simulations show that injection of electrons at these densities can be assisted through ionization induced trapping in a mix of Helium with 3% Oxygen.

The scintillation properties of powders and single-crystals of BaFI doped with Eu2+ are presented. Single crystals were grown by the vertical Bridgman technique. Under optical and X-ray excitation, the samples exhibit a narrow E2+ 5d-4f transition emission centered at 405 nm. The scintillation light output is estimated to be 55,000+-5,000 photons/MeV at 662 keV with 85percent of the light decaying within 600 ns. An energyresolution of 8.5percent full width at half maximum (FWHM) has been achieved using this scintillator for 662 keV excitation (137Cs source) at room temperature.

We investigate the effects of non-equilibrium particle distributions resulting from rapid deuterium-tritium burning in plasmas using a Fokker-Planck code that incorporates small-angle Coulomb scattering, Brehmsstrahlung, Compton scattering, and thermal-nuclear burning. We find that in inertial confinement fusion environments, deviations away from Maxwellian distributions for either deuterium or tritium ions are small and result in 1% changes in the energy production rates. The deuterium and tritium effective temperatures are not equal, but differ by only about 2.5% near the time of peak burn rate. Simulations with high Z (Xe) dopants show that the dopant temperature closely tracks that of the fuel. On the other hand, fusion product ion distributions are highly non-Maxwellian, and careful treatments of energy-exchange between these ions and other particles is important for determining burn rates.

None

The reaction of excess HSiCl{sub 3} with the aforementioned triamines led to the formation of [Si{sub 6}Cl{sub 14}]{sup 2-} containing salts in all instances. The isolated complex salts were characterized using FT-IR and elemental analysis. IR spectra of these compounds showed characteristic Si-H stretching modes around 2100cm{sup -1} due to the hexacoordinate silane cation and Si-Cl active modes near 528cm{sup -1} as a result of the cyclic dianion. Reaction yields and elemental analysis (CHN) of the salts are summarized in a table. The reaction of peralkylated triamines with HSiCl{sub 3} in dry CH{sub 2}Cl{sub 2} gives ionic compounds based upon the tetradecachlorocyclohexasilane dianion. Several substituted triamines(R{sub 2}NC{sub 2}H{sub 4}NR{prime}C{sub 2}H{sub 4}NR{sub 2}where R = R{prime} = Et, {sup n}Pr; R = Et, R{prime}= {sup n}Bu, {sup n}Hexyl, Benzyl) were examined for this reaction and N,N,N{prime},N{prime}-tetraethyl-N{sup {double_prime}}-benzyl-diethylenetriamine produced the best yields of [Si{sub 6}Cl{sub 14}]{sup 2-} salt at 23% based on the amine reagent. This improvement in yield could be attributed to the decreased nucleophilicity of the central amine through increased steric hindrance of the alkyl substituents. The overall consequence of this substituent variation study has revealed new reagents for the synthesis of [Si{sub 6}Cl{sub 14}]{sup 2-} salts and further demonstrated …

Herein we demonstrate a novel electroless etching synthesis of monolithic, single-crystalline, mesoporous silicon nanowire arrays with a high surface area and luminescent properties consistent with conventional porous silicon materials. The photoluminescence of these nanowires suggest they are composed of crystalline silicon with small enough dimensions such that these arrays may be useful as photocatalytic substrates or active components of nanoscale optoelectronic devices. A better understanding of this electroless route to mesoporous silicon could lead to facile and general syntheses of different narrow bandgap semiconductor nanostructures for various applications.

The objective of the CERTS Microgrid Test Bed project was to enhance the ease of integrating energy sources into a microgrid. The project accomplished this objective by developing and demonstrating three advanced techniques, collectively referred to as the CERTS Microgrid concept, that significantly reduce the level of custom field engineering needed to operate microgrids consisting of generating sources less than 100kW. The techniques comprising the CERTS Microgrid concept are: 1) a method for effecting automatic and seamless transitions between grid-connected and islanded modes of operation, islanding the microgrid's load from a disturbance, thereby maintaining a higher level of service, without impacting the integrity of the utility's electrical power grid; 2) an approach to electrical protection within a limited source microgrid that does not depend on high fault currents; and 3) a method for microgrid control that achieves voltage and frequency stability under islanded conditions without requiring high-speed communications between sources. These techniques were demonstrated at a full-scale test bed built near Columbus, Ohio and operated by American Electric Power. The testing fully confirmed earlier research that had been conducted initially through analytical simulations, then through laboratory emulations,and finally through factory acceptance testing of individual microgrid components. The islanding and resychronization …

LOCO has been a powerful beam-based diagnostics and optics control method for storage rings and synchrotrons worldwide ever since it was established at NSLS by J. Safranek. This method measures the orbit response matrix and optionally the dispersion function of the machine. The data are then fitted to a lattice model by adjusting parameters such as quadrupole and skew quadrupole strengths in the model, BPM gains and rolls, corrector gains and rolls of the measurement system. Any abnormality of the machine that affects the machine optics can then be identified. The resulting lattice model is equivalent to the real machine lattice as seen by the BPMs. Since there are usually two or more BPMs per betatron period in modern circular accelerators, the model is often a very accurate representation of the real machine. According to the fitting result, one can correct the machine lattice to the design lattice by changing the quadrupole and skew quadrupole strengths. LOCO is so important that it is routinely performed at many electron storage rings to guarantee machine performance, especially after the Matlab-based LOCO code became available. However, for some machines, LOCO is not easy to carry out. In some cases, LOCO fitting converges to …

We describe recent advances in the demonstration of table-top full field microscopes that use soft x-ray lasers for illumination. We have achieved wavelength resolution and single shot exposure operation with a very compact 46.9 nm microscope based on a desk-top size capillary discharge laser. This {lambda}-46.9 nm microscope has been used to capture full field images of a variety of nanostructure systems and surfaces. In a separate development we have demonstrated a zone plate microscope that uses {lambda}=13.2 nm laser illumination to image absorption defects in an extreme ultraviolet lithography (EUVL) mask in the same geometry used in a 4x demagnification EUVL stepper. Characterization of the microscope’s transfer function shows it can resolve 55 nm half period patterns. With these capabilities, the {lambda}-13.2 nm microscope is well suited for evaluation of pattern and defect printability of EUVL masks for the 22 nm node.

This report talks about Caustic Cleaning for Waste Heel Removal

Complexation of U(VI) with fluoride at elevated temperatures in aqueous solutions was studied by spectrophotometry. Four successive complexes, UO{sub 2}F{sup +}, UO{sub 2}F{sub 2}(aq), UO{sub 2}F{sub 3}{sup -}, and UO{sub 2}F{sub 4}{sup 2-}, were identified, and the stability constants at 25, 40, 55, and 70 C were calculated. The stability of the complexes increased as the temperature was elevated. The enthalpies of complexation at 25 C were determined by microcalorimetry. Thermodynamic parameters indicate that the complexation of U(VI) with fluoride in aqueous solutions at 25 to 70 C is slightly endothermic and entropy-driven. The Specific Ion Interaction (SIT) approach was used to obtain the thermodynamic parameters of complexation at infinite dilution. Structural information on the U(VI)/fluoride complexes was obtained by extended X-ray absorption fine structure spectroscopy.

The SPS at high intensities exhibits transverse single-bunch instabilities with signatures consistent with an Ecloud driven instability. While the SPS has a coupled-bunch transverse feedback system, control of Ecloud-driven motion requires a much wider control bandwidth capable of sensing and controlling motion within each bunched beam. This paper draws beam dynamics data from the measurements and simulations of this SPS instability, and estimates system requirements for a feedback system with 2-4 GS/sec. sampling rates to damp Ecloud-driven transverse motion in the SPS at intensities desired for high-current LHC operation.

The time when energy-related carbon emissions come overwhelmingly from developed countries is coming to a close. China has already overtaken the United States as the world's leading emitter of greenhouse gas emissions. The economic growth that China has experienced is not expected to slow down significantly in the long term, which implies continued massive growth in energy demand. This paper draws on the extensive expertise from the China Energy Group at LBNL on forecasting energy consumption in China, but adds to it by exploring the dynamics of demand growth for electricity in the residential sector -- and the realistic potential for coping with it through efficiency. This paper forecasts ownership growth of each product using econometric modeling, in combination with historical trends in China. The products considered (refrigerators, air conditioners, fans, washing machines, lighting, standby power, space heaters, and water heating) account for 90percent of household electricity consumption in China. Using this method, we determine the trend and dynamics of demandgrowth and its dependence on macroeconomic drivers at a level of detail not accessible by models of a more aggregate nature. In addition, we present scenarios for reducing residential consumption through efficiency measures defined at the product level. The research …

None

Katzenstein and Apt investigate the important question of pollution emission reduction benefits from variable generation resources such as wind and solar. Their methodology, which couples an individual variable generator to a dedicated gas plant to produce a flat block of power is, however, inappropriate. For CO{sub 2}, the authors conclude that variable generators 'achieve {approx} 80% of the emission reductions expected if the power fluctuations caused no additional emissions.' They find even lower NO{sub x} emission reduction benefits with steam-injected gas turbines and a 2-4 times net increase in NO{sub x} emissions for systems with dry NO{sub x} control unless the ratio of energy from natural gas to variable plants is greater than 2:1. A more appropriate methodology, however, would find a significantly lower degradation of the emissions benefit than suggested by Katzenstein and Apt. As has been known for many years, models of large power system operations must take into account variable demand and the unit commitment and economic dispatch functions that are practiced every day by system operators. It is also well-known that every change in wind or solar power output does not need to be countered by an equal and opposite change in a dispatchable resource. The …

Minimizing plutonium measurement uncertainty is essential to nuclear material control and international safeguards. In 2005, the International Organization for Standardization (ISO) published ISO 12183 'Controlled-potential coulometric assay of plutonium', 2nd edition. ISO 12183:2005 recommends a target of {+-}0.01% for the mass of original sample in the aliquot because it is a critical assay variable. Mass measurements in radiological containment were evaluated and uncertainties estimated. The uncertainty estimate for the mass measurement also includes uncertainty in correcting for buoyancy effects from air acting as a fluid and from decreased pressure of heated air from the specific heat of the plutonium isotopes.

None

Polyurethane foam has been employed in impact limiters for large radioactive materials packagings since the early 1980's. Its consistent crush response, controllable structural properties and excellent thermal insulating characteristics have made it attractive as replacement for the widely used cane fiberboard for smaller, drum size packagings. Accordingly, polyurethane foam was chosen for the overpack material for the 9977 and 9978 packagings. The study reported here was undertaken to provide data to support the analyses performed as part of the development of the 9977 and 9978, and compared property values reported in the literature with published property values and test results for foam specimens taken from a prototype 9977 packaging. The study confirmed that, polyurethane foam behaves in a predictable and consistent manner and fully satisfies the functional requirements for impact absorption and thermal insulation.