Publications

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Experimental studies have been performed on the velocity-field characteristics of AlGaN/GaN heterostructures. A pulsed voltage input in combination with a four-point measurement was used in a 50 {Omega} environment to determinethe drift velocity of electrons in the two-dimensional electron gas as a function of the applied electric field. These measurements show an apparent saturation velocity near 3.1 x 10{sub 7} cm/s, at a field of 140 kV/cm. A comparison of these studies shows that the experimental velocities are close to previously published simulations based upon Monte Carlo techniques.

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Nonuniformities in both sheath electric field and plasma excitation were observed around dissimilar metals placed on a rf electrode. Spatial maps of the rf sheath electric field obtained by laser-induced fluorescence-dip (LIF-dip) spectroscopy show that the sheath structure was a function of the electrode metal. In addition to the electric-field measurements, LIF, optical emission, and Langmuir probe measurements show nonuniform excitation around the dissimilar metals. The degree and spatial extent of the discharge nonuniformities were dependent on discharge conditions and the history of the metal surfaces.

We use quantum mechanics to characterize the structure and current-voltage performance of the Stoddart-Heath rotaxane-based programmable electronic switch. We find that the current when the ring is on the DNP is 37?58 times the current when the ring is on the TTF, in agreement with experiment (ratio of 10?100). This establishes the basis for iterative experimental?theoretical efforts to optimize systems for molecule-based electronics which we illustrate by predicting the effect of adding a group such as CN to the rotaxane.

The mechanism of hydroarylation of olefins by a homogeneous Ph-Ir(acac){sub 2}(L) catalyst is elucidated by first principles quantum mechanical methods (DFT), with particular emphasis on activation of the catalyst, catalytic cycle, and interpretation of experimental observations. On the basis of this mechanism, we suggest new catalysts expected to have improved activity. Initiation of the catalyst from the inert trans-form into the active cis-form occurs through a dissociative pathway with a calculated {Delta}H(0 K){sub {+-}} = 35.1 kcal/mol and {Delta}G(298 K){sub {+-}} = 26.1 kcal/mol. The catalytic cycle features two key steps, 1,2-olefin insertion and C?H activation via a novel mechanism, oxidative hydrogen migration. The olefin insertion is found to be rate determining, with a calculated {Delta}H(0 K){sub {+-}} = 27.0 kcal/mol and {Delta}G(298 K){sub {+-}} = 29.3 kcal/mol. The activation energy increases with increased electron density on the coordinating olefin, as well as increased electron-donating character in the ligand system. The regioselectivity is shown to depend on the electronic and steric characteristics of the olefin, with steric bulk and electron withdrawing character favoring linear product formation. Activation of the C?H bond occurs in a concerted fashion through a novel transition structure best described as an oxidative hydrogen migration. The character of the transition structure is seven coordinate Ir{sup V}, with a full bond formed between the migrating hydrogen and iridium. Several experimental observations are investigated and explained: (a) The nature of L influences the rate of the reaction through a ground-state effect. (b) The lack of {beta}-hydride products is due to kinetic factors, although {beta}-hydride elimination is calculated to be facile, all further reactions are kinetically inaccessible. (c) Inhibition by excess olefin is caused by competitive binding of olefin and aryl starting materials during the catalytic cycle in a statistical fashion. On the basis of this insertion-oxidative hydrogen transfer mechanism we suggest that electron-withdrawing substituents on the acac ligands, such as trifluoromethyl groups, are good modifications for catalysts with higher activity.

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In this paper, weak formulations and finite element discretizations of the governing partial differential equations of three-dimensional nonlinear acoustics in absorbing fluids are presented. The fluid equations are considered in an Eulerian framework, rather than a displacement framework, since in the latter case the corresponding finite element formulations suffer from spurious modes and numerical instabilities. When taken with the governing partial differential equations of a solid body and the continuity conditions, a coupled formulation is derived. The change in solid/fluid interface conditions when going from a linear acoustic fluid to a nonlinear acoustic fluid is demonstrated. Finite element discretizations of the coupled problem are then derived, and verification examples are presented that demonstrate the correctness of the implementations. We demonstrate that the time step size necessary to resolve the wave decreases as steepening occurs. Finally, simulation results are presented on a resonating acoustic cavity, and a coupled elastic/acoustic system consisting of a fluid-filled spherical tank.

Calculations of specific contact resistance as a function of doping and barrier height were performed for p-type GaN. These calculations took into account two valence bands, each with different effective masses, and show that at low doping, the heavy hole band accounts for most of the conduction, whereas at heavier doping, the light hole band dominates conduction. These calculations also indicate the barrier height for typical contacts to p-GaN is between 0.75 eV and 1 eV. Specific contact resistance measurements were made for oxidized Ni/Au, Pd, and oxidized Ni/Pd ohmic contact metal schemes to p-GaN. The Ni/Pd contact had the lowest specific contact resistance, 6 x 10{sup -4} {Omega} cm{sup 2}. Auger sputter depth profile analysis showed some Ni diffused away from the GaN surface to the contact surface with the bulk of the Pd located in between two areas of Ni. Both Ni and Pd interdiffused with the GaN at the semiconductor surface. The majority of the oxygen observed was with the Ni as NiO. Angle-resolved-x-ray photoelectron spectroscopy (AR-XPS) analyses showed the formation of predominantly NiO and PdO species, with higher Ni and Pd oxides at the contact surface.

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We used molecular dynamics simulations to study the adsorption of aqueous uranyl species (UO22+) onto clay mineral surfaces in the presence of sodium counterions and carbonato ligands. The large system size (10 000 atoms) and long simulation times (10 ns) allowed us to investigate the thermodynamics of ion adsorption, and the atomistic detail provided clues for the observed adsorption behavior. The model system consisted of the basal surface of a low-charge Na-montmorillonite clay in contact with aqueous uranyl carbonate solutions with concentrations of 0.027 M, 0.081 M, and 0.162 M. Periodic boundary conditions were used in the simulations to better represent an aqueous solution interacting with an external clay surface. Uranyl adsorption tendency was found to decrease as the aqueous uranyl carbonate concentration was increased, while sodium adsorption remained constant. The observed behavior is explained by physical and chemical effects. As the ionic strength of the aqueous solution was increased, electrostatic factors prevented further uranyl adsorption once the surface charge had been neutralized. Additionally, the formation of aqueous uranyl carbonate complexes, including uranyl carbonato oligomers, contributed to the decreased uranyl adsorption tendency.

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We have used scanning tunneling microscopy and low-energy electron microscopy to measure the thermal decay of two-dimensional Cu, Pb-overlayer, and Pb-Cu alloy islands on Pb-Cu(1 1 1) surface alloys. Decay rates covering 6-7 orders of magnitude are accessible by applying the two techniques to the same system. We find that Cu adatom diffusion across the surface alloy is rate-limiting for the decay of both Pb and Pb-Cu islands on the surface alloy and that this rate decreases monotonically with increasing Pb concentration in the alloy. The decrease is attributed to repulsive interactions between Cu adatoms and embedded Pb atoms in the surface alloy. The measured temperature dependences of island decay rates are consistent with first-principles calculations of the Cu binding and diffusion energies related to this 'site-blocking' effect.

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We investigate the liquid structure, ion hydration, and some thermodynamic properties associated with the rigid geometry approximation to water by applying ab initio molecular dynamics simulations (AIMD) with the Perdew-Burke-Ernzerhof (PBE) exchange-correlation functional at T = 320 K. We vary the rigid water geometry in order to locate a class of practical water models that yield reasonable liquid structure and dynamics, and to examine the progression of AIMD-predicted water behavior as the OH bond length varies. Water constrained at the optimal PBE gas phase geometry yields reasonable pair correlation functions. The predicted liquid phase pressure, however, is large ({approx}8.0 kbar). Although the O-H bond in water should elongate when transferred from gas to the condensed phase, when it is constrained to 0.02, or even just 0.01 {angstrom} longer than the optimal gas phase value, liquid water is predicted to be substantially overstructured compared to experiments. Zero temperature calculations of the thermodynamic properties of cubic ice underscore the sensitivity toward small variations in the O-H bond length. We examine the hydration structures of potassium, chloride, and formate ions in one rigid PBE water model. The results are in reasonable agreement with unconstrained AIMD simulations.

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Microorganisms are ubiquitous in subsurface environments and play a major role in the biogeochemical recycling of various elements. In this paper, we have developed a general approach for a systematic evaluation of microbial impact on the long-term performance of the repository. We have demonstrated that data on microbial population alone are not sufficient for the evaluation of microbial impact on repository performance and a sensible approach for such evaluation must be based on the consideration of environmental constraints on microbial reaction pathways. We have applied our approach to both the Yucca Mountain (YM) repository and the Waste Isolation Pilot Plant (WIPP). We have demonstrated that the effect of microbial activity on the near-field chemistry in the Yucca Mountain repository is negligible because of limited nutrient supply and harsh environmental conditions created by waste emplacement. Whereas for the WIPP, we have shown that, due to the presence of a large quantity of organic materials and nutrients in the wastes, a significant microbial activity can potentially be stimulated and its impact on repository performance can be evaluated with carefully designed incubation experiments coupled with performance assessment calculations. The impact of microbial gas generation on disposal room chemistry in the WIPP can be mitigated by introducing MgO as a backfill material.

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This work reports on the grafting of methyl methacrylate polymer brushes containing spirobenzopyran pendant groups from flat silica surfaces and colloidal particles utilizing atom transfer radical polymerization (ATRP). The reaction conditions were optimized with respect to the kind of surface bound initiator, the type of halide and ligand used in the catalytic complex, the presence/absence of untethered initiator, and solvent type. This enabled synthesis of coatings up to 80 {+-} 3 nm thick with controlled spirobenzopyran content. While polymerization kinetics indicate the presence of chain termination reactions, the 'living' character of the process is confirmed by controlled formation of block copolymer brushes. UV/vis spectroscopy was used to characterize the UV-induced isomerization of spirobenzopyran to zwitterionic merocyanine and the thermal back-reaction. Spectral and kinetic analyses of this latter bleaching process points to the existence of free and associated merocyanines in the polymeric brush in both tetrahydrofuran and toluene. However, stabilization of merocyanine species by the polymer matrix is considerably greater in toluene with thermal back-reaction rates approaching those determined for solid dry films.

Colloidal particles were derivatized with end-grafted polymethylmethacryate polymer brushes containing varying concentrations of spirobenzopyran photochromic molecules. The polymers were grown from initiator-functionalized silica partilces by an atom-transfer radical polymerization (ATRP). These core-shell colloids formed stable suspensions in toluene with the spirobenzopyran in its closed, nonpolar form. However, UV-induced photoswitching of the photochrome to its open, polar merocyanine isomer caused rapid aggregation. The nature of this colloidal stability transition was examined with respect to the spirobenzopyran content in the polymeric brush and solvent polarity. Turbidimetry, wettability studies, UV-vis spectroscopy, suspension rheology, SEM, and visual inspection were utilized to characterize the system photoswitchability. It was found that the system exhibiting the greatest transition in toluene was the copolymer brush composed of 20% spirobenzopyran and 80% methyl methacrylate.

Quartz surfaces and colloidal silica particles were derivatized with a poly(methyl methacrylate) copolymer containing spirobenzopyran (SP) photochromic molecules in the pendant groups at a concentration of 20 mol %. Two-photon near-IR excitation ({approx}780 nm) was then used to create chemically distinct patterns on the modified surfaces through a photochromic process of SP transformation to the zwitterionic merocyanine (MC) isomer. The derivatized colloids were approximately 10 times more likely to adsorb onto the photoswitched, MC regions. Surface coverage and adsorption kinetics have been compared to the mean-field model of irreversible monolayer adsorption.

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This report examines the design process of a photovoltaic (solar) based power supply for wireless sensor networks. Such a system stores the energy produced by an array of photovoltaic cells in a secondary (rechargeable) battery that in turn provides power to the individual node of the sensor network. The goal of such a power supply is to enable a wireless sensor network to have an autonomous operation on the order of years. Ideally, such a system is as small as possible physically while transferring the maximum amount of available solar energy to the load (the node). Within this report, there is first an overview of current solar and battery technologies, including characteristics of different technologies and their impact on overall system design. Second is a general discussion of modeling, predicting, and analyzing the extended operation of a small photovoltaic power supply and setting design parameters. This is followed by results and conclusions from the testing of a few basic systems. Lastly, some advanced concepts that may be considered in order to optimize future systems will be discussed.

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In this paper we present a two-level overlapping domain decomposition preconditioner for the finite-element discretization of elliptic problems in two and three dimensions. The computational domain is partitioned into overlapping subdomains, and a coarse space correction, based on aggregation techniques, is added. Our definition of the coarse space does not require the introduction of a coarse grid. We consider a set of assumptions on the coarse basis functions to bound the condition number of the resulting preconditioned system. These assumptions involve only geometrical quantities associated with the aggregates and the subdomains. We prove that the condition number using the two-level additive Schwarz preconditioner is O(H/{delta} + H{sub 0}/{delta}), where H and H{sub 0} are the diameters of the subdomains and the aggregates, respectively, and {delta} is the overlap among the subdomains and the aggregates. This extends the bounds presented in [C. Lasser and A. Toselli, Convergence of some two-level overlapping domain decomposition preconditioners with smoothed aggregation coarse spaces, in Recent Developments in Domain Decomposition Methods, Lecture Notes in Comput. Sci. Engrg. 23, L. Pavarino and A. Toselli, eds., Springer-Verlag, Berlin, 2002, pp. 95-117; M. Sala, Domain Decomposition Preconditioners: Theoretical Properties, Application to the Compressible Euler Equations, Parallel Aspects, Ph.D. thesis, Ecole Polytechnique Federale de Lausanne, Lausanne, Switzerland, 2003; M. Sala, Math. Model. Numer. Anal., 38 (2004), pp. 765-780]. Numerical experiments on a model problem are reported to illustrate the performance of the proposed preconditioner.

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In recent years, efforts have been made within the nuclear weapons complex (National Nuclear Security Administration) of the Department of Energy (DOE) to replace Resource Conservation and Recovery Act (RCRA) regulated solvents (i.e., flammable, toxic, corrosive, and reactive) and ozone-depleting chemicals (ODC) with more benign alternatives. Within the National Nuclear Security Administration (NNSA) and the Department of Defense (DoD) sectors, these solvents are used for cleaning hardware during routine maintenance operations. A primary goal of this study is to replace flammable solvents used in wiping applications. Two cleaners, including a hydrofluoroether (HFE) and an azeotrope of the HFE and isopropyl alcohol (IPA), have been studied as potential replacements for flammable solvents. Cleaning efficacy, short-term and long-term materials compatibility, corrosion, drying times, flammability, environment, safety and health (ES&H) and accelerated aging issues were among the experiments used to screen candidate solvents by the interagency team performing this work. This report presents cleaning efficacy results as determined by the contact angle Goniometer as well as materials compatibility results of various metal alloys and polymers. The results indicate that IPA (baseline cleaner) and the HFE/IPA azeotrope are roughly equivalent in their ability to remove fluorinated grease, silicone grease, and a simulated finger print contaminant from various metal alloys. All of the ASTM sandwich and immersion corrosion tests with IPA, HFE or the HFE/IPA azeotrope on metal alloys showed no signs of corrosion. Furthermore, no deleterious effects were noted for polymeric materials immersed in IPA, HFE, or the HFE/IPA azeotrope.

The annual program report provides detailed information about all aspects of the SNL/CA Hazardous Materials Management Program for a given calendar year. It functions as supporting documentation to the SNL/CA Environmental Management System Program Manual. The 2005 program report describes the activities undertaken during the past year, and activities planned in future years to implement the Hazardous Materials Management Program, one of six programs that supports environmental management at SNL/CA.

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This manual describes the use of theXyceParallel Electronic Simulator.Xycehasbeen designed as a SPICE-compatible, high-performance analog circuit simulator, andhas been written to support the simulation needs of the Sandia National Laboratorieselectrical designers. This development has focused on improving capability over thecurrent state-of-the-art in the following areas:%04Capability to solve extremely large circuit problems by supporting large-scale par-allel computing platforms (up to thousands of processors). Note that this includessupport for most popular parallel and serial computers.%04Improved performance for all numerical kernels (e.g., time integrator, nonlinearand linear solvers) through state-of-the-art algorithms and novel techniques.%04Device models which are specifically tailored to meet Sandia's needs, includingmany radiation-aware devices.3 XyceTMUsers' Guide%04Object-oriented code design and implementation using modern coding practicesthat ensure that theXyceParallel Electronic Simulator will be maintainable andextensible far into the future.Xyceis a parallel code in the most general sense of the phrase - a message passingparallel implementation - which allows it to run efficiently on the widest possible numberof computing platforms. These include serial, shared-memory and distributed-memoryparallel as well as heterogeneous platforms. Careful attention has been paid to thespecific nature of circuit-simulation problems to ensure that optimal parallel efficiencyis achieved as the number of processors grows.The development ofXyceprovides a platform for computational research and de-velopment aimed specifically at the needs of the Laboratory. WithXyce, Sandia hasan %22in-house%22 capability with which both new electrical (e.g., device model develop-ment) and algorithmic (e.g., faster time-integration methods, parallel solver algorithms)research and development can be performed. As a result,Xyceis a unique electricalsimulation capability, designed to meet the unique needs of the laboratory.4 XyceTMUsers' GuideAcknowledgementsThe authors would like to acknowledge the entire Sandia National Laboratories HPEMS(High Performance Electrical Modeling and Simulation) team, including Steve Wix, CarolynBogdan, Regina Schells, Ken Marx, Steve Brandon and Bill Ballard, for their support onthis project. We also appreciate very much the work of Jim Emery, Becky Arnold and MikeWilliamson for the help in reviewing this document.Lastly, a very special thanks to Hue Lai for typesetting this document with LATEX.TrademarksThe information herein is subject to change without notice.Copyrightc 2002-2003 Sandia Corporation. All rights reserved.XyceTMElectronic Simulator andXyceTMtrademarks of Sandia Corporation.Orcad, Orcad Capture, PSpice and Probe are registered trademarks of Cadence DesignSystems, Inc.Silicon Graphics, the Silicon Graphics logo and IRIX are registered trademarks of SiliconGraphics, Inc.Microsoft, Windows and Windows 2000 are registered trademark of Microsoft Corporation.Solaris and UltraSPARC are registered trademarks of Sun Microsystems Corporation.Medici, DaVinci and Taurus are registered trademarks of Synopsys Corporation.HP and Alpha are registered trademarks of Hewlett-Packard company.Amtec and TecPlot are trademarks of Amtec Engineering, Inc.Xyce's expression library is based on that inside Spice 3F5 developed by the EECS De-partment at the University of California.All other trademarks are property of their respective owners.ContactsBug Reportshttp://tvrusso.sandia.gov/bugzillaEmailxyce-support%40sandia.govWorld Wide Webhttp://www.cs.sandia.gov/xyce5 XyceTMUsers' GuideThis page is left intentionally blank6

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Transmission electron microscopy and x-ray diffraction were used to assess the microstructure and strain of Al{sub x}Ga{sub 1?x}N(x = 0.61-0.64) layers grown on AlN. The compressively-strained AlGaN is partially relaxed by inclined threading dislocations, similar to observations on Si-doped AlGaN by P. Cantu, F. Wu, P. Waltereit, S. Keller, A. E. Romanov, U. K. Mishra, S. P. DenBaars, and J. S. Speck [Appl. Phys. Lett. 83, 674 (2003) ]; however, in our material, the dislocations bend before the introduction of any Si. The bending may be initiated by the greater lattice mismatch or the lower dislocation density of our material, but the presence of Si is not necessarily required. The relaxation by inclined dislocations is quantitatively accounted for with the model of A. E. Romanov and J. S. Speck [Appl. Phys. Lett. 83, 2569 (2003)], and we demonstrate the predicted linear dependence of relaxation on layer thickness. Notably, such relaxation was not found in tensile strained AlGaN grown on GaN [J. A. Floro, D. M. Follstaedt, P. Provencio, S. J. Hearne, and S. R. Lee, J. Appl. Phys. 96, 7087 (2004)], even though the same mechanism appears applicable.

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We have created a logic-based, Turing-complete language for stochastic modeling. Since the inference scheme for this language is based on a variant of Pearl's loopy belief propagation algorithm, we call it Loopy Logic. Traditional Bayesian networks have limited expressive power, basically constrained to finite domains as in the propositional calculus. Our language contains variables that can capture general classes of situations, events and relationships. A first-order language is also able to reason about potentially infinite classes and situations using constructs such as hidden Markov models(HMMs). Our language uses an Expectation-Maximization (EM) type learning of parameters. This has a natural fit with the Loopy Belief Propagation used for inference since both can be viewed as iterative message passing algorithms. We present the syntax and theoretical foundations for our Loopy Logic language. We then demonstrate three examples of stochastic modeling and diagnosis that explore the representational power of the language. A mechanical fault detection example displays how Loopy Logic can model time-series processes using an HMM variant. A digital circuit example exhibits the probabilistic modeling capabilities, and finally, a parameter fitting example demonstrates the power for learning unknown stochastic values.

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The C6 project 'Encapsulation Processes' has been designed to obtain experimental measurements for discovery of phenomena critical to improving these processes, as well as data required in the verification and validation plan (Rao et al. 2001) for model validation of flow in progressively complex geometries. We have observed and recorded the flow of clear, Newtonian liquids and opaque, rheologically complex suspensions in two mold geometries. The first geometry is a simple wineglass geometry in a cylinder and is reported here in Part 1. The results in a more realistic encapsulation geometry are reported in Part 2.

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Diagnostic tracer layers of Al and/or Mg have been embedded in Dynamic Hohlraum targets which are imploded on Sandia National Laboratories Z generator by surrounding them with nested arrays of tungsten wires. The K-shell lines of these elements are observed, usually in absorption, in both time-resolved and time-integrated spectra. The radiation physics of line formation in this environment is well understood and captured with a detailed model. A {chi}{sup 2} fit to the measured line intensities is used in conjunction with the model to determine the hohlraums intrinsic properties. Among other features, our analyses find no evidence of intrinsic top-bottom asymmetry in the Dynamic Hohlraums.

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Dipicolinic acid (DPA, 2,6-pyridinedicarboxylic acid) is a substance uniquely present in bacterial spores such as that from anthrax (B. anthracis). It is known that DPA can be detected by the long-lived fluorescence of its terbium chelate; the best limit of detection (LOD) reported thus far using a large benchtop gated fluorescence instrument using a pulsed Xe lamp is 2 nM. We use a novel AlGaN light-emitting diode (LED) fabricated on a sapphire substrate that has peak emission at 291 nm. Although the overlap of the emission band of this LED with the absorption band of Tb-DPA ({lambda}{sub max} doublet: 273, 279 nm) is not ideal, we demonstrate that a compact detector based on this LED and an off-the-shelf gated photodetection module can provide an LOD of 0.4 nM, thus providing a basis for convenient early warning detectors.

Deuterated p-type GaN(Mg,{sup 2}H) films were irradiated at room temperature with 1 MeV protons to create native point defects with a concentration approximately equal to the Mg doping (5 x 10{sup 19} cm{sup -3}). The samples were then annealed isothermally at a succession of temperatures while monitoring the infrared absorption due to the H local mode of the MgH defect. As the samples were annealed, the MgH absorption signal decreased and a new mode at slightly higher frequency appeared, which has been associated with the approach of a mobile nitrogen interstitial. We used the time dependence of the MgH absorption to obtain a diffusion barrier of the nitrogen interstitial in p-type GaN of 1.99 eV. This is in good agreement with theoretical calculations of nitrogen interstitial motion in GaN.

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X-ray spectra and images from Al (with 5% of Mg and some with 5% of NaF dopants) and Cu (pure and with 4% of Ni) wire arrays and X-pinches were accumulated in experiments on the 1 MA pulsed power generator at UNR. In particular, axially and radially resolved K-shell X-ray spectra of Al, Mg, and Na and L-shell X-ray spectra of Cu and Ni were recorded by a KAP crystal (in a spectral region from 6 to 15 Aring) through different slits from 50 mum to 3 mm. In addition, spatially integrated harder X-ray spectra were monitored by a LiF crystal. Non-LTE kinetic models of Al, Mg, and Na, and of Cu and Ni provided spatially resolved electron temperatures and densities for experiments with Al and Cu loads, respectively. Advantages of using alloys and dopants with small concentrations for spectroscopic plasma diagnostics will be presented. Dependence of the plasma's spatial structures, temperatures, and densities from wire material and load configurations, sizes, and masses will be discussed .

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The purpose of this report is to provide school administrators with the ability to determine their security system requirements, so they can make informed decisions when working with vendors and others to improve their security posture. This is accomplished by (1) explaining a systems-based approach to defining the objectives and needs of the system, and (2), providing information on the ability of common components (sensors, cameras, metal detectors, etc) to achieve those objectives, in an effectively integrated system.

This document describes the specimen and transportation containers currently available for use with hazardous and infectious materials. A detailed comparison of advantages, disadvantages, and costs of the different technologies is included. Short- and long-term recommendations are also provided.3 DraftDraftDraftExecutive SummaryThe Federal Bureau of Investigation's Hazardous Materials Response Unit currently has hazardous material transport containers for shipping 1-quart paint cans and small amounts of contaminated forensic evidence, but the containers may not be able to maintain their integrity under accident conditions or for some types of hazardous materials. This report provides guidance and recommendations on the availability of packages for the safe and secure transport of evidence consisting of or contaminated with hazardous chemicals or infectious materials. Only non-bulk containers were considered because these are appropriate for transport on small aircraft. This report will addresses packaging and transportation concerns for Hazardous Classes 3, 4, 5, 6, 8, and 9 materials. If the evidence is known or suspected of belonging to one of these Hazardous Classes, it must be packaged in accordance with the provisions of 49 CFR Part 173. The anthrax scare of several years ago, and less well publicized incidents involving unknown and uncharacterized substances, has required that suspicious substances be sent to appropriate analytical laboratories for analysis and characterization. Transportation of potentially hazardous or infectious material to an appropriate analytical laboratory requires transport containers that maintain both the biological and chemical integrity of the substance in question. As a rule, only relatively small quantities will be available for analysis. Appropriate transportation packaging is needed that will maintain the integrity of the substance, will not allow biological alteration, will not react chemically with the substance being shipped, and will otherwise maintain it as nearly as possible in its original condition.The recommendations provided are short-term solutions to the problems of shipping evidence, and have considered only currently commercially available containers. These containers may not be appropriate for all cases. Design, testing, and certification of new transportation containers would be necessary to provide a container appropriate for all cases.Table 1 provides a summary of the recommendations for each class of hazardous material.Table 1: Summary of RecommendationsContainerCost1-quart paint can with ArmlockTM seal ringLabelMaster(r)%242.90 eachHazard Class 3, 4, 5, 8, or 9 Small ContainersTC Hazardous Material Transport ContainerCurrently in Use4 DraftDraftDraftTable 1: Summary of Recommendations (continued)ContainerCost55-gallon open or closed-head steel drumsAll-Pak, Inc.%2458.28 - %2473.62 eachHazard Class 3, 4, 5, 8, or 9 Large Containers95-gallon poly overpack LabelMaster(r)%24194.50 each1-liter glass container with plastic coatingLabelMaster(r)%243.35 - %243.70 eachHazard Class 6 Division 6.1 Poisonous by Inhalation (PIH) Small ContainersTC Hazardous Material Transport ContainerCurrently in Use20 to 55-gallon PIH overpacksLabelMaster(r)%24142.50 - %24170.50 eachHazard Class 6 Division 6.1 Poisonous by Inhalation (PIH) Large Containers65 to 95-gallon poly overpacksLabelMaster(r)%24163.30 - %24194.50 each1-liter transparent containerCurrently in UseHazard Class 6 Division 6.2 Infectious Material Small ContainersInfectious Substance ShipperSource Packaging of NE, Inc.%24336.00 eachNone Commercially AvailableN/AHazard Class 6 Division 6.2 Infectious Material Large ContainersNone Commercially Available N/A5

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Experimental results are presented for stress evolution, in vacuum and electrolyte, for the first monolayer of Cu on Au(111). In electrolyte the monolayer is pseudomorphic and the stress-thickness change is -0.60 N/m, while conventional epitaxy theory predicts a value of +7.76 N/m. In vacuum, the monolayer is incoherent with the underlying gold. Using a combination of first-principles based calculations and molecular dynamic simulations we analyzed these results and demonstrate that in electrolyte, overlayer coherency is maintained owing to anion adsorption.

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We apply density functional theory (DFT) and the DFT+U technique to study the adsorption of transition metal porphine molecules on atomistically flat Au(111) surfaces. DFT calculations using the Perdew?Burke?Ernzerhof exchange correlation functional correctly predict the palladium porphine (PdP) low-spin ground state. PdP is found to adsorb preferentially on gold in a flat geometry, not in an edgewise geometry, in qualitative agreement with experiments on substituted porphyrins. It exhibits no covalent bonding to Au(111), and the binding energy is a small fraction of an electronvolt. The DFT+U technique, parametrized to B3LYP-predicted spin state ordering of the Mn d-electrons, is found to be crucial for reproducing the correct magnetic moment and geometry of the isolated manganese porphine (MnP) molecule. Adsorption of Mn(II)P on Au(111) substantially alters the Mn ion spin state. Its interaction with the gold substrate is stronger and more site-specific than that of PdP. The binding can be partially reversed by applying an electric potential, which leads to significant changes in the electronic and magnetic properties of adsorbed MnP and 0.1 {angstrom} changes in the Mn-nitrogen distances within the porphine macrocycle. We conjecture that this DFT+U approach may be a useful general method for modeling first-row transition metal ion complexes in a condensed-matter setting.

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We developed a pyrometer that operates near the high-temperature bandgap of GaN, thus solving the transparency problem once a {approx} 1 {micro}m thick GaN epilayer has been established. The system collects radiation in the near-UV (380-415 nm) and has an effective detection wavelength of {approx}405 nm. By simultaneously measuring reflectance we also correct for emissivity changes when films of differing optical properties (e.g. AlGaN) are deposited on the GaN template. We recently modified the pyrometer hardware and software to enable measurements in a multiwafer Veeco D-125 OMVPE system. A method of synchronizing and indexing the detection system with the wafer platen was developed; so signals only from the desired wafer(s) could be measured, while rejecting thermal emission signals from the platen. Despite losses in optical throughput and duty cycle we are able to maintain adequate performance from 700 to 1100 C.

We present the solution of a 1D radial MHD model of the plasma ablated from multi-MA wire array implosions extending a recently obtained steady state solution [J.P. Chittenden, et al. Phys. Plasmas 11, 1118 (2004)] to a driving current that is exponential in time. We obtain a solution for the flow in almost analytical form by reducing the partial differential equations to a set of ordinary differential equations with a single parameter. We compute the mass weighted density width, and find the regime in which it agrees to a few percent with that of a simpler approximation to the ablated plasma flow, for which the driving current is linear in time, and the flow velocity constant. Assuming that the density width at the end of the ablation period is proportional to width of the plasma sheath at stagnation, we obtain a scaling relationship for peak X-ray power. We compare this relationship to experimental peak X-ray powers for tungsten wire arrays on the Z pulsed power generator of Sandia National Laboratories, and to previously proposed scaling hypotheses. We also use this scaling to project peak X-ray powers on ZR, a higher peak current modification of Z, presently under design.

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Summary from only given. The capabilities of the Z accelerator will be significantly enhanced by the Z Refurbishment (ZR) project [McDaniel DH, 2002]. The performance of a single ZR module is currently being characterized in the pre-production engineering evaluation test bed, Z20 [Lehr, JM, 2003]. Z20 is thoroughly diagnosed so that electrical performance of the module can be established. Circuit models of Z20 have been developed and validated in both Screamer [1985] and Bertha [1989] circuit codes. For the purposes of predicting ZR performance, a full ZR circuit model has also been developed in Bertha. The full ZR model (using operating parameters demonstrated on Z20) indicates that the required 26 MA, 100 ns implosion time, output load current pulse will be achieved on ZR. In this paper, the electrical characterization of Z20 and development of the single module circuit models will be discussed in detail. The full ZR model will also be discussed and the results of several system studies conducted to predict ZR performance will be presented.

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The stress evolution during electrodeposition of NiMn from a sulfamate-based bath was investigated as a function of Mn concentration and current density. The NiMn stress evolution with film thickness exhibited an initial high transitional stress region followed by a region of steady-state stress with a magnitude that depended on deposition rate, similar to the previously reported stress evolution in electrodeposited Ni [S. J. Hearne and J. A. Floro, J. Appl. Phys. 97, 014901-1 (2005)]. The incorporation of increasing amounts of Mn resulted in a linear increase in the steady-state stress at constant current density. However, no significant changes in the texture or grain size were observed, which indicates that an atomistic process is driving the changes in steady-state stress. Additionally, microstrain measured by ex situ x-ray diffraction increased with increasing Mn content, which was likely the result of localized lattice distortions associated with substitutional incorporation of Mn and/or increased twin density.

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The summary of this report is: (1) The Kernal Density Estimator (KDE) model using log data provides the most conservative estimates; (2) The Empirical Tolerance Limit (ETL) model provides the least conservative estimates; (3) The results for the Karhunen-Loeve (K-L) and Normal Tolerance Limit (NTL) models lie in between the extremes; (4) The NTL results ended up being as credible as any of the other methods. This may be related to the fact that the data appeared to fit a lognormal distribution for higher values of {beta}; (5) The discrepancy between these methods appears to widen for higher values of {beta} and {gamma}; (6) The reasons for the extreme difference in the KDE results depending on whether one uses the raw data or the log of the data is not clear at this time; and (7) Which model will best suit our needs is not clear at this time.

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Blue-emitting, cubic phase CdSe nanorods with an approximate diameter of 2.5 nm and lengths up to 12 nm have been synthesized at low temperature (100 °C) in a single surfactant using a single-source molecular precursor. Transmission electron microscopy and dynamic light scattering measurements indicate that the nanorods are formed from self-assembly of isotropic nanoclusters. Anisotropic growth in a single surfactant appears to be favored when growth occurs below the thermal decomposition temperature of the single-source precursor. © 2005 American Chemical Society.

Sodium aluminum hydrides have gained attention due to their high hydrogen weight percent (5.5% ideal) compared to interstitial hydrides, and as a model for hydrides with even higher hydrogen weight fraction. The purpose of this paper is to investigate the Ti-compounds that are formed under solution-doping techniques, such as wet doping in solvents such as tetrahydrofuran (THF). Compound formation in Ti-doped sodium aluminum hydrides is investigated using X-ray diffraction (XRD) and magic angle spinning (MAS) nuclear magnetic resonance (NMR). We present lattice parameter measurements of crushed single crystals, which were exposed to Ti during growth. Rietveld refinements indicate no lattice parameter change and thus no solubility for Ti in NaAlH4 by this method of exposure. In addition, X-ray diffraction data indicate that no Ti substitutes in NaH, the final decomposition product for the alanate. Reaction products of completely reacted (33.3 at.%-doped) samples that were solvent-mixed or mechanically milled are investigated. Formation of TiAl 3 is observed in mechanically milled materials, but not solution mixed samples, where bonding to THF likely stabilizes Ti-based nano-clusters. The Ti in these clusters is activated by mechanical milling. © 2004 Elsevier B.V. All rights reserved.

Three-dimensional Direct Simulation Monte Carlo simulations of Columbia Shuttle Orbiter flight STS-107 are presented. The aim of this work is to determine the aerodynamic and heating behavior of the Orbiter during aerobraking maneuvers and to provide piecewise integration of key scenario events to assess the plausibility of the candidate failure scenarios. The flight of the Orbiter is examined at two altitudes: 350 kft and 300 kft. The flow field around the Orbiter and the heat transfer to it are calculated for the undamaged configuration. The flow inside the wing for an assumed damage to the leading edge in the form of a 10-inch hole is studied. © 2005 American Institute of Physics.

For gas flows in microfluidic configurations, the Knudsen layer close to the wall can comprise a substantial part of the entire flowfield and has a major effect on quantities such as the mass flow rate through micro devices. The Knudsen layer itself is characterized by a highly nonlinear relationship between the viscous stress and the strain rate of the gas, so even if the Navier-Stokes equations can be used to describe the core gas flow they are certainly inappropriate for the Knudsen layer itself. In this paper we propose a "wall-function" model for the stress/strain rate relations in the Knudsen layer. The constitutive structure of the Knudsen layer has been derived from results from kinetic theory for isothermal shear flow over a planar surface. We investigate the ability of this simplified model to predict Knudsen-layer effects in a variety of configurations. We further propose a semi-empirical Knudsen-number correction to this wall function, based on high-accuracy DSMC results, to extend the predictive capabilities of the model to greater degrees of rarefaction. © 2005 American Institute of Physics.

Gain properties of GaInNAs lasers with different nitrogen concentrations in the quantum wells are investigated experimentally and theoretically. Whereas nitrogen incorporation induces appreciable modifications in the spectral extension and the carrier density dependence of the gain, it is found that the linewidth enhancement factor is reduced by inclusion of nitrogen, but basically unaffected by different nitrogen content due to the balancing between gain and index changes. © 2005 American Institute of Physics.

The implementation of variational transition state theory (VTST) for long-range asymptotic potential forms is considered, with particular emphasis on the energy and total angular momentum resolved (μJ -VTST) implementation. A long-range transition state approximation yields a remarkably simple and universal description of the kinetics of reactions governed by long-range interactions. The resulting (μJ -VTST) implementation is shown to yield capture-rate coefficients that compare favorably with those from trajectory simulations (deviating by less than 10%) for a wide variety of neutral and ionic long-range potential forms. Simple analytic results are derived for many of these cases. A brief comparison with a variety of low-temperature experimental studies illustrates the power of this approach as an analysis tool. The present VTST approach allows for a simple analysis of the applicability conditions for some related theoretical approaches. It also provides an estimate of the temperature or energy at which the "long-range transition state" moves to such short separations that short-range effects, such as chemical bonding, steric repulsion, and electronic state selectivity, must be considered. © 2005 American Institute of Physics.

The chemical and structural changes within thin films of (3-glycidoxypropyl)trimethoxysilane (GPS) after exposure for various periods of time to air saturated with either D 2O or H 2O at 80°C were studied. The X-ray and neutron reflectivity (XR and NR), combined wuth attenuated total reflection infrared (ATR-IR) spectroscopy were used. The chemical degradation mechanism was identified by IR as hydrolysis of siloxane bonds. GPS films were prepared by dip-coating, which resulted in a greater and more variable thickness than for the spin-coated samples, for ATR-IR. The little changes in the reflectivity data was observed for films conditioned with D 2O at 80°C for one month.

Identifying the areas to be protected is an important part of the development of measures for physical protection against sabotage at complex nuclear facilities. In June 1999, the International Atomic Energy Agency published INFCIRC/225/Rev.4, 'The Physical Protection of Nuclear Material and Nuclear Facilities.' This guidance recommends that 'Safety specialists, in close cooperation with physical protection specialists, should evaluate the consequences of malevolent acts, considered in the context of the State's design basis threat, to identify nuclear material, or the minimum complement of equipment, systems or devices to be protected against sabotage.' This report presents a structured, transparent approach for identifying the areas that contain this minimum complement of equipment, systems, and devices to be protected against sabotage that is applicable to complex nuclear facilities. The method builds upon safety analyses to develop sabotage fault trees that reflect sabotage scenarios that could cause unacceptable radiological consequences. The sabotage actions represented in the fault trees are linked to the areas from which they can be accomplished. The fault tree is then transformed (by negation) into its dual, the protection location tree, which reflects the sabotage actions that must be prevented in order to prevent unacceptable radiological consequences. The minimum path sets of this fault tree dual yield, through the area linkage, sets of areas, each of which contains nuclear material, or a minimum complement of equipment, systems or devices that, if protected, will prevent sabotage. This method also provides guidance for the selection of the minimum path set that permits optimization of the trade-offs among physical protection effectiveness, safety impact, cost and operational impact.

Most attempts to quantify differential diffusion (DD) are based on the difference between different definitions of the mixture fraction. This paper presents a general method for evaluating differential diffusion in premixed or nonpremixed systems based on conservation equations for the elemental mass fractions. These measures form a basis for analysing differential diffusion. Casting these in terms of a mixture fraction gives particular insight into differential diffusion for nonpremixed systems, and provides a single DD measure. Furthermore, it allows direct evaluation of the validity of the traditional assumptions involved in writing a mixture fraction transport equation. Results are presented for one-dimensional opposed flow simulations of hydrogen and methane flames as well as direct numerical simulations (DNS) of CH4/H2-air and CO/H2-air flames. For a common definition of the mixture fraction, the DD measure can be approximated well by considering only the contribution of H2 and CH4 in methane-air flames. Differential diffusion is largely driven by production of H2 in the flame zone for hydrocarbon flames. Effects of strain rate and filter width on the relative importance of differential diffusion are examined. © 2005 Taylor & Francis Group Ltd.

Rapid microchip reversed-phase HPLC of peptides and proteins at pressure gradients of 12 bar/cm (180 psi/cm) has been performed using a microdevice that integrates subnanoliter on-chip injection and separation with a miniaturized fluorescence detector. Proteins and peptides were separated on a C18 side-chain porous polymer monolith defined by contact lithography, and injection was achieved via a pressure-switchable fluoropolymer valve defined using projection lithography. Preliminary separations of peptide standards and protein mixtures were performed in 40-200 s, and switching between samples with no detectible sample carryover has been performed. The injections and separations were reproducible; the relative standard deviation (RSD) for retention time was 0.03%, and peak area RSD was 3.8%. Sample volumes ranging from 220 to 800 pL could be linearly metered by controlling the pressure injection pulse duration with conventional timing and valving. The current prototype system shows the potential for rapid and autonomous HPLC separations with varying modalities and the potential for direct connection to mass spectrometers at nanospray flow rates. © 2005 American Chemical Society.

We have determined limits on the cross section for both electronically nonadiabatic excitation and quenching in the Cl (Pj2) + D2 system. Our experiment incorporates crossed-molecular-beam scattering with state-selective Cl (P 12,32 2) detection and velocity-mapped ion imaging. By colliding atomic chlorine with D2, we address the propensity for collisions that result in a change of the spin-orbit level of atomic chlorine either through electronically nonadiabatic spin-orbit excitation Cl (P 32 2) + D2 → Cl* (P 12 2) + D2 or through electronically nonadiabatic spin-orbit quenching Cl* (P 12 2) + D2 →Cl (P 32 2) + D2. In the first part of this report, we estimate an upper limit for the electronically nonadiabatic spin-orbit excitation cross section at a collision energy of 5.3 kcalmol, which lies above the energy of the reaction barrier (4.9 kcalmol). Our analysis and simulation of the experimental data determine an upper limit for the excitation cross section as σNA ≤0.012 Å2. In the second part of this paper we investigate the propensity for electronically nonadiabatic spin-orbit quenching of Cl * following a collision with D2 or He. We perform these experiments at collision energies above and below the energy of the reaction barrier. By comparing the amount of scattered Cl* in our images to the amount of Cl* lost from the atomic beam we obtain the maximum cross section for electronically nonadiabatic quenching as σNA ≤ 15 -15 +44 Å2 for a collision energy of 7.6 kcalmol. Our experiments show the probability for electronically nonadiabatic quenching in Cl* + D2 to be indistinguishable to that for the kinematically identical system of Cl* +He. © 2005 American Institute of Physics.

This report is the latest in a continuing series that highlights the recent technical accomplishments associated with the work being performed within the Materials and Process Sciences Center. Our research and development activities primarily address the materials-engineering needs of Sandia's Nuclear-Weapons (NW) program. In addition, we have significant efforts that support programs managed by the other laboratory business units. Our wide range of activities occurs within six thematic areas: Materials Aging and Reliability, Scientifically Engineered Materials, Materials Processing, Materials Characterization, Materials for Microsystems, and Materials Modeling and Simulation. We believe these highlights collectively demonstrate the importance that a strong materials-science base has on the ultimate success of the NW program and the overall DOE technology portfolio.

Iron, the most ubiquitous of the transition metals and the fourth most plentiful element in the Earth's crust, is the structural backbone of our modern infrastructure. It is therefore ironic that as a nanoparticle, iron has been somewhat neglected in favor of its own oxides, as well as other metals such as cobalt, nickel, gold, and platinum. This is unfortunate, but understandable. Iron 's reactivity is important in macroscopic applications (particularly rusting), but is a dominant concern at the nanoscale. Finely divided iron has long been known to be pyrophoric, which is a major reason that iron nanoparticles have not been more fully studied to date. This extreme reactivity has traditionally made iron nanoparticles difficult to study and inconvenient for practical applications. Iron however has a great deal to offer at the nanoscale, including very potent magnetic and catalytic properties. Recent work has begun to take advantage of iron's potential, and work in this field appears to be blossoming. © 2005 Wiley-VCH Verlag GmbH & Co. KGaA.

This Final Report on the Monitoring Phase of the former Weeks Island Strategic Petroleum Reserve crude oil storage facility details the results of five years of monitoring of various surface accessible quantities at the decommissioned facility. The Weeks Island mine was authorized by the State of Louisiana as a Strategic Petroleum Reserve oil storage facility from 1979 until decommissioning of the facility in 1999. Discovery of a sinkhole over the facility in 1992 with freshwater inflow to the facility threatened the integrity of the oil storage and led to the decision to remove the oil, fill the chambers with brine, and decommission the facility. Thereafter, a monitoring phase, by agreement between the Department of Energy and the State, addressed facility stability and environmental concerns. Monitoring of the surface ground water and the brine of the underground chambers from the East Fill Hole produced no evidence of hydrocarbon contamination, which suggests that any unrecovered oil remaining in the underground chambers has been contained. Ever diminishing progression of the initial major sinkhole, and a subsequent minor sinkhole, with time was verification of the response of sinkholes to filling of the facility with brine. Brine filling of the facility ostensively eliminates any further growth or new formation from freshwater inflow. Continued monitoring of sinkhole response, together with continued surface surveillance for environmental problems, confirmed the intended results of brine pressurization. Surface subsidence measurements over the mine continued throughout the monitoring phase. And finally, the outward flow of brine was monitored as a measure of the creep closure of the mine chambers. Results of each of these monitoring activities are presented, with their correlation toward assuring the stability and environmental security of the decommissioned facility. The results suggest that the decommissioning was successful and no contamination of the surface environment by crude oil has been found.

Goal of this study was to develop and characterize novel polymeric materials as pseudostationary phases in electrokinetic chromatography. Fundamental studies have characterized the chromatographic selectivity of the materials as a function of chemical structure and molecular conformation. The selectivities of the polymers has been studied extensively, resulting in a large body of fundamental knowledge regarding the performance and selectivity of polymeric pseudostationary phases. Two polymers have also been used for amino acid and peptide separations, and with laser induced fluorescence detection. The polymers performed well for the separation of derivatized amino acids, and provided some significant differences in selectivity relative to a commonly used micellar pseudostationary phase. The polymers did not perform well for peptide separations. The polymers were compatible with laser induced fluorescence detection, indicating that they should also be compatible with chip-based separations.

The recent interests in developing multiscale model-based simulation procedures have brought about the challenging tasks of bridging different spatial and temporal scales within a unified framework. However, the research focus has been on the scale effect in the spatial domain with the loading rate being assumed to be quasi-static. Although material properties are rate-dependent in nature, little has been done in understanding combined loading rate and specimen size effects on the material properties at different scales. In addition, the length and time scales that can be probed by the molecular level simulations are still fairly limited due to the limitation of computational capability. Based on the experimental and computational capabilities available, therefore, an attempt is made in this report to formulate a hyper-surface in both spatial and temporal domains to predict combined size and rate effects on the mechanical properties of engineering materials. To demonstrate the features of the proposed hyper-surface, tungsten specimens of various sizes under various loading rates are considered with a focus on the uniaxial loading path. The mechanical responses of tungsten specimens under other loading paths are also explored to better understand the size effect. It appears from the preliminary results that the proposed procedure might provide an effective means to bridge different spatial and temporal scales in a unified multiscale modeling framework, and facilitate the application of nanoscale research results to engineering practice.

Power sources capable of supplying tens of watts are needed for a wide variety of applications including portable electronics, sensors, micro aerial vehicles, and mini-robotics systems. The utility of these devices is often limited by the energy and power density capabilities of batteries. A small combustion engine using liquid hydrocarbon fuel could potentially increase both power and energy density by an order of magnitude or more. This report describes initial development work on a meso-scale external combustion engine based on the Stirling cycle. Although other engine designs perform better at macro-scales, we believe the Stirling engine cycle is better suited to small-scale applications. The ideal Stirling cycle requires efficient heat transfer. Consequently, unlike other thermodynamic cycles, the high heat transfer rates that are inherent with miniature devices are an advantage for the Stirling cycle. Furthermore, since the Stirling engine uses external combustion, the combustor and engine can be scaled and optimized semi-independently. Continuous combustion minimizes issues with flame initiation and propagation. It also allows consideration of a variety of techniques to promote combustion that would be difficult in a miniature internal combustion engine. The project included design and fabrication of both the engine and the combustor. Two engine designs were developed. The first used a cylindrical piston design fabricated with conventional machining processes. The second design, based on the Wankel rotor geometry, was fabricated by through-mold electroforming of nickel in SU8 and LIGA micromolds. These technologies provided the requisite precision and tight tolerances needed for efficient micro-engine operation. Electroformed nickel is ideal for micro-engine applications because of its high strength and ductility. A rotary geometry was chosen because its planar geometry was more compatible with the fabrication process. SU8 lithography provided rapid prototypes to verify the design. A final high precision engine was created via LIGA. The micro-combustor was based on an excess enthalpy concept. Development of a micro-combustor included both modeling and experiments. We developed a suite of simulation tools both in support of the design of the prototype combustors, and to investigate more fundamental aspects of combustion at small scales. Issues of heat management and integration with the micro-scale Stirling engine were pursued using CFD simulations. We found that by choice of the operating conditions and channel dimensions energy conversion occurs by catalysis-dominated or catalysis-then-homogeneous phase combustion. The purpose of the experimental effort in micro-combustion was to study the feasibility and explore the design parameters of excess enthalpy combustors. The efforts were guided by the necessity for a practical device that could be implemented in a miniature power generator, or as a stand-alone device used for heat generation. Several devices were fabricated and successfully tested using methane as the fuel.

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We have synthesized defect-free aluminosilicate and silicalite zeolite thin films supported on commercially available alpha and gamma alumina disk substrates. We have also built a permeation unit that can test both pure and mixed gases from room temperature to 250 C. Results indicate fluxes on the order of 10{sup -6} to 10{sup -7} mole/(m{sup 2}Pa sec) and excellent separation values for H{sub 2} or CO{sub 2}. For the Al/Si membrane: H{sub 2}/N{sub 2} {ge} 61, H{sub 2}/CO{sub 2} {ge} 80, H{sub 2}/CH{sub 4} = 7, CH{sub 4}/CO{sub 2} {ge} 11; for the TPA/Si membrane: H{sub 2}/N{sub 2} {ge} 61, H{sub 2}/CO{sub 2} {ge} 80, H{sub 2}/CH{sub 4} = 7, CH{sub 4}/CO{sub 2} {ge} 11. Our data show that we can use the adsorption ability plus the effective pore diameter of the zeolite to 'tune' the selectivity of the membrane. Another avenue of research is into bulk novel molecular sieve materials, with the goal of 'tuning' pore sizes to molecular sieving needs. A novel crystalline 12-ring microporous gallophosphate material is described.

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Binding of porphyrin to murine ferrochelatase, the terminal enzyme of the heme biosynthetic pathway, is investigated by employing a set of variants harboring mutations in a putative porphyrin-binding loop. Using resonance Raman (RR) spectroscopy, the structural properties of the ferrochelatase-bound porphyrins are examined, especially with respect to the porphyrin deformation occurring in the environment of the active site. This deformation is thought to be a key step in the enzymatic insertion of ferrous iron into the porphyrin ring to make heme. Our previous RR spectroscopic studies of binding of porphyrin to murine ferrochelatase led us to propose that the wild-type enzyme induces porphyrin distortion even in the absence of the metal ion substrate. Here, we broaden this view by presenting evidence that the degree of a specific nonplanar porphyrin deformation contributes to the catalytic efficiency of ferrochelatase and its variants. The results also suggest that the conserved Trp256 (murine ferrochelatase numbering) is partially responsible for the observed porphyrin deformation. Binding of porphyrin to the ferrochelatase variants causes a decrease in the intensity of RR out-of-plane vibrational mode {gamma}{sub 15}, a saddling-like mode that is strong in the wild-type enzyme. In particular, the variant with a catalytic efficiency 1 order of magnitude lower than that of the wild-type enzyme is estimated to produce less than 30% of the wild-type saddling deformation. These results suggest that specific conserved loop residues (especially Trp256) are directly involved in the saddling of the porphyrin substrate.

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In contrast to traditional terascale simulations that have known, fixed data inputs, dynamic data-driven (DDD) applications are characterized by unknown data and informed by dynamic observations. DDD simulations give rise to inverse problems of determining unknown data from sparse observations. The main difficulty is that the optimality system is a boundary value problem in 4D space-time, even though the forward simulation is an initial value problem. We construct special-purpose parallel multigrid algorithms that exploit the spectral structure of the inverse operator. Experiments on problems of localizing airborne contaminant release from sparse observations in a regional atmospheric transport model demonstrate that 17-million-parameter inversion can be effected at a cost of just 18 forward simulations with high parallel efficiency. On 1024 Alphaserver EV68 processors, the turnaround time is just 29 minutes. Moreover, inverse problems with 135 million parameters - corresponding to 139 billion total space-time unknowns - are solved in less than 5 hours on the same number of processors. These results suggest that ultra-high resolution data-driven inversion can be carried out sufficiently rapidly for simulation-based 'real-time' hazard assessment.

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Accurate and efficient turbulence simulation in complex geometries is a formidable chal-lenge. Traditional methods are often limited by low accuracy and/or restrictions to simplegeometries. We explore the merger of Discontinuous Galerkin (DG) spatial discretizationswith Variational Multi-Scale (VMS) modeling, termed Local VMS (LVMS), to overcomethese limitations. DG spatial discretizations support arbitrarily high-order accuracy on un-structured grids amenable for complex geometries. Furthermore, high-order, hierarchicalrepresentation within DG provides a natural framework fora prioriscale separation crucialfor VMS implementation. We show that the combined benefits of DG and VMS within theLVMS method leads to promising new approach to LES for use in complex geometries.The efficacy of LVMS for turbulence simulation is assessed by application to fully-developed turbulent channelflow. First, a detailed spatial resolution study is undertakento record the effects of the DG discretization on turbulence statistics. Here, the localhp[?]refinement capabilites of DG are exploited to obtain reliable low-order statistics effi-ciently. Likewise, resolution guidelines for simulating wall-bounded turbulence using DGare established. We also explore the influence of enforcing Dirichlet boundary conditionsindirectly through numericalfluxes in DG which allows the solution to jump (slip) at thechannel walls. These jumps are effective in simulating the influence of the wall commen-surate with the local resolution and this feature of DG is effective in mitigating near-wallresolution requirements. In particular, we show that by locally modifying the numericalviscousflux used at the wall, we are able to regulate the near-wall slip through a penaltythat leads to improved shear-stress predictions. This work, demonstrates the potential ofthe numerical viscousflux to act as a numerically consistent wall-model and this successwarrents future research.As in any high-order numerical method some mechanism is required to control aliasingeffects due to nonlinear interactions and to ensure nonlinear stability of the method. Inthis context, we evaluate the merits of two approaches to de-aliasing -- spectralfilteringand polynomial dealiasing. While both approaches are successful, polynomial-dealiasingis found to be better suited for use in large-eddy simulation. Finally, results using LVMSare reported and show good agreement with reference direct numerical simulation therebydemonstrating the effectiveness of LVMS for wall-bounded turbulence. This success pavesthe way for future applications of LVMS to more complex turbulentflows.3

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Flow-generated noise, especially rotorcraft noise has been a serious concern for bothcommercial and military applications. A particular important noise source for rotor-craft is Blade-Vortex-Interaction (BVI)noise, a high amplitude, impulsive sound thatoften dominates other rotorcraft noise sources. Usually BVI noise is caused by theunsteady flow changes around various rotor blades due to interactions with vorticespreviously shed by the blades. A promising approach for reducing the BVI noise isto use on-blade controls, such as suction/blowing, micro-flaps/jets, and smart struc-tures. Because the design and implementation of such experiments to evaluate suchsystems are very expensive, efficient computational tools coupled with optimal con-trol systems are required to explore the relevant physics and evaluate the feasibilityof using various micro-fluidic devices before committing to hardware.In this thesis the research is to formulate and implement efficient computationaltools for the development and study of optimal control and design strategies for com-plex flow and acoustic systems with emphasis on rotorcraft applications, especiallyBVI noise control problem. The main purpose of aeroacoustic computations is todetermine the sound intensity and directivity far away from the noise source. How-ever, the computational cost of using a high-fidelity flow-physics model across thefull domain is usually prohibitive and itmight also be less accurate because of thenumerical diffusion and other problems. Taking advantage of the multi-physics andmulti-scale structure of this aeroacoustic problem, we develop a multi-model, multi-domain (near-field/far-field) method based on a discontinuous Galerkin discretiza-tion. In this approach the coupling of multi-domains and multi-models is achievedby weakly enforcing continuity of normal fluxes across a coupling surface. For ourinterested aeroacoustics control problem, the adjoint equations that determine thesensitivity of the cost functional to changes in control are also solved with same ap-proach by weakly enforcing continuity ofnormal fluxes across a coupling surface.Such formulations have been validated extensively for several aeroacoustics state andcontrol problems.A multi-model based optimal control framework has been constructed and ap-plied to our interested BVI noise control problem. This model problem consists ofthe interaction of a compressible vortex with Bell AH-1 rotor blade with wall-normal3 velocity used as control on the rotor blade surface. The computational domain isdecomposed into the near-field and far-field. The near-field is obtained by numericalsolution of the Navier-Stokes equations while far away from the noise source, wherethe effect of nonlinearities is negligible, the linearized Euler equations are used tomodel the acoustic wave propagation. The BVI wave packet is targeted by definingan objective function that measures the square amplitude of pressure fluctuations inan observation region, at a time interval encompassing the dominant leading edgecompressibility waves. Our control results show that a 12dB reduction in the ob-servation region is obtained. Interestingly, the control mechanism focuses on theobservation region and only minimize the sound level in that region at the expense ofother regions. The vortex strength and trajectory get barely changed. However, theoptimal control does alter the interaction of the vortical and potential fields, whichis the source of BVI noise. While this results in a slight increase in drag, there is asignificant reduction in the temporal gradient of lift leading to a reduction in BVIsound levels.4

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Catamount is designed to be a low overhead operating system for a parallel computing environment. Functionality is limited to the minimum set needed to run a scientific computation. The design choices and implementations will be presented. A massively parallel processor (MPP), high performance computing (HPC) system is particularly sensitive to operating system overhead. Traditional, multi-purpose, operating systems are designed to support a wide range of usage models and requirements. To support the range of needs, a large number of system processes are provided and are often interdependent on each other. The overhead of these processes leads to an unpredictable amount of processor time available to a parallel application. Except in the case of the most embarrassingly parallel of applications, an MPP application must share interim results with its peers before it can make further progress. These synchronization events are made at specific points in the application code. If one processor takes longer to reach that point than all the other processors, everyone must wait. The overall finish time is increased. Sandia National Laboratories began addressing this problem more than a decade ago with an architecture based on node specialization. Sets of nodes in an MPP are designated to perform specific tasks, each running an operating system best suited to the specialized function. Sandia chose to not use a multi-purpose operating system for the computational nodes and instead began developing its first light weight operating system, SUNMOS, which ran on the compute nodes on the Intel Paragon system. Based on its viability, the architecture evolved into the PUMA operating system. Intel ported PUMA to the ASCI Red TFLOPS system, thus creating the Cougar operating system. Most recently, Cougar has been ported to Cray's XT3 system and renamed to Catamount. As the references indicate, there are a number of descriptions of the predecessor operating systems. While the majority of those discussions still apply to Catamount, this paper takes a fresh look at the architecture as it is currently implemented.

Abstract not provided.